Review

pubs.acs.org/CR

Potassium−Sodium Niobate Lead-Free Piezoelectric Materials: Past,

Present, and Future of Phase Boundaries
Jiagang Wu,* Dingquan Xiao, and Jianguo Zhu
Department of Materials Science, Sichuan University, Chengdu 610064, China
4.5.9. Sintering Aids and Sintering Atmos-
phere 2580
4.6. Extrinsic Factors 2581
4.6.1. Density vs Electrical Properties 2581
4.6.2. Grain Morphology vs Electrical Proper-
ties 2582
4.6.3. Domain Structure vs Electrical Proper-
ties 2582
CONTENTS 5. Relationship between Phase Boundaries and
Piezoelectricity 2583
1. Introduction 2559 6. Applications of KNN-Based Materials 2584
2. Background of Phase Boundaries 2562 6.1. Piezoelectric Energy Harvesting 2584
3. Characterization Tools of Phase Boundaries 2563 6.2. Piezoelectric Actuator 2584
3.1. High-Resolution Synchrotron X-ray Diffrac- 7. Outlook and Future Work 2585
tion 2564 7.1. Designing New Phase Boundaries 2585
3.2. Neutron Diffraction 2564 7.2. Analyzing Phase Compositions 2585
3.3. Transmission Electron Microscopy 2564 7.3. Physical Origin of High Piezoelectricity 2585
3.4. Spectroscopic Techniques 2564 7.4. Intrinsic Characteristics of Phase Boundaries 2586
3.4.1. Raman Spectroscopy 2564 7.5. Investigating the Stability of Piezoelectricity 2586
3.4.2. Infrared Spectroscopy 2565 7.6. Other Issues 2586
3.5. Theoretical Methods 2565 8. Conclusions 2586
3.6. Combined Tools 2565 Author Information 2586
4. Type and Construction of Phase Boundaries 2566 Corresponding Author 2586
4.1. Orthorhombic−Tetragonal Phase Bounda- Notes 2586
ries 2566 Biographies 2586
4.1.1. Li+ Substitution 2566 Acknowledgments 2586
4.1.2. Li+ and Sb5+ Substitution 2567 References 2587
4.1.3. Li+ and Ta5+ Substitution 2567
4.1.4. Li+, Sb5+, and Ta5+ Substitution 2568
4.1.5. Addition of ABO3 2568 1. INTRODUCTION
4.1.6. Addition of ABO3 Multicomponents 2569
4.1.7. Ratio of K/Na 2570 High-performance piezoceramics are some of the most
4.1.8. Other Ions 2570 important and widely used materials, and as such research
4.2. Rhombohedral−Orthorhombic Phase Boun- into this topic is at the forefront of high-technology advanced
daries 2570 materials.1−19 Since the 1950s, (PbZr1−xTixO3, PZT)-based
4.3. Rhombohedral−Tetragonal Phase Bounda- ceramics have been given much attention due to their excellent
ries 2572 piezoelectric constants (d33 ≈ 200−750 pC/N) and high Curie
4.4. Dopant Engineering 2574 temperatures (TC = 180−320 °C) (see Figure 1) and are
4.4.1. Doping with Equipollent Metals 2574 currently applied in many electronic devices (e.g., sensors,
4.4.2. Doping with Aliovalent Metals 2574 actuators, ultrasound transducers, etc.).4,5,7−11,20,21 However,
4.5. Supplementary Tools 2575 the lead content (∼60 wt %) of PZT raises environmental
4.5.1. Sintering Temperature 2576 concerns during their preparation, process, and even dis-
4.5.2. Reactive Template Grain Growth Meth- posal.4,5,7−11,20,21 For maintaining socially sustainable develop-
od 2576 ment, regions and countries have put a great deal of effort into
4.5.3. Spark-Plasma Sintering 2576 the research and development (R&D) of lead-free piezoelectric
4.5.4. Nonstoichiometry 2577 materials, and moreover, the related laws and regulations have
4.5.5. Two-Step Sintering 2577 been legislated or improved.22−34 For example, the European
4.5.6. Single Crystals 2578 Union passed the Restriction of Hazardous Substances (RoHS)
4.5.7. Thin Films 2580
4.5.8. Poling Conditions 2580 Received: December 1, 2014
Published: March 20, 2015

© 2015 American Chemical Society 2559 DOI: 10.1021/cr5006809

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Chemical Reviews
Figure 1. d33 and TC of PZT-based ceramics.
law in 2003, the “Household Electronic Products Recycling
Law” was passed in Japan, and the “Electronic Information
Product Pollution Control Management Regulation” was
established in China in 2006. Although the lead content of
piezoelectric devices and some capacitors is currently exempted
due to related technical questions, the validity of this exemption
treaty will expire in July 2016. As a result, the R&D of lead-free
piezoelectrics has become urgent under current international
legislature.1−3,14−19,35−285
Among these lead-free candidates, (K,Na)NbO3 (KNN) has
become one of the most extensively investigated piezoelectric
systems in the past 10 years due to its large d33 and high
TC.12,17,97,101,102,104,106 Recently, a number of countries have
invested considerable manpower and financial resources into
the study of KNN-based piezoelectrics, and some significant
breakthroughs have been achieved.12,101,105−118,166,256,260,262
For example, Satio et al. observed a large d33 value (∼416
pC/N) in (K,Na,Li)(Nb,Ta,Sb)O3-textured ceramics fabricated
using reactive templated grain growth (RTGG) methods.12 In
the meantime, Cross commented that Satio’s work may allow
us to be “Lead-free at last”.100 Guo et al.,101,102 meanwhile, also
observed enhanced piezoelectricity (d33 = 200−235 pC/N) in
KNN ceramics by doping LiNbO3 or LiTaO3 using conven-
tional solid-state methods. In these studies, their d33 values can
be promoted to be several times that of a pure KNN ceramic,3
and the involved phase boundaries play a large part in their
improved piezoelectricity (refs 12, 16−18, 97, 101, 105−119,
166, 251, 256, 260, and 262). In 2014, we developed new
KNN-based material systems with large piezoelectricity (d33 ≈
490 pC/N) by designing new phase boundaries consisiting of
rhombohedral and tetragonal (R−T) phases;106 moreover, this
material was able to demonstrate both a large d33 and a high TC
through refining of its composition,106−118,256,260 further
increasing research interest in KNN-based piezoelectrics.
Figure 2 displays statistics related to refereed publications on
lead-free piezoceramics from 2004 to 2014 using the keywords
“lead-free” and “piezoelectric”. We classified the referenced
publications according to the keywords “lead-free piezo-
electric”, “alkali niobium-based”, and “construction of alkali
niobium-based materials”, as shown in Figure 2. There is a
gradually increasing trend in the number of publications
concerning alkali niobium-based materials, among which the
construction of phase boundaries has become a prominent tool
for the improvement of their electrical properties. The
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Figure 2. Publications on lead-free piezoceramics in refereed journals
for the time range from 2004 to 2014 (collected from ISI Web of
Science with the keywords “lead-free” and “piezoelectric”).
statistical results indicate that alkali niobium-based materials
have received a great amount of attention.12,90−285 To better
understand this situation, we counted the percentage of the
publications according to the data of Figure 2, as plotted in
Figure 3a and 3b. Publications on alkali niobium materials make
Figure 3. (a) Publications on alkali niobium-based and lead-free
piezoceramics in refereed journals for the time range from 2004 to
2014; (b) publications on lead-free piezoceramics with phase
boundary construction and others.
up ∼43.85% of those on lead-free piezoelectrics, and moreover,
those concerned with the construction of phase boundaries
comprise 53.27%. As a result, phase boundaries play an
important role in the development of alkali niobium lead-free
piezoelectrics as a whole. In the past, the “morphotropic phase
boundary” was also used to realize a major breakthrough in the
study of the piezoelectric activity of PZT.4,5 Generally speaking,
the piezoelectric activity of KNN-based ceramics is still inferior
to that of most PZT materials (see Figure 1), and thus, further
breakthroughs must be achieved by extensively replacing lead-
based materials in some applications. As mentioned above, the
construction of phase boundaries will be key to realizing the
enhanced piezoelectricity of KNN compared to PZT; thus, it is
necessary to review the developments of phase boundaries in
the field of KNN-based materials for further promotion of the
piezoelectric activity and to guide our studies.
In the past 10 years, researchers have reviewed the advances
of KNN-based materials from different view-
points,16−19,96−98,103−105,266,267 greatly accelerating research
progress.16−19,103−120 For example, the relationships between
microstructure (domain wall) and properties concerning lead-
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Figure 4. Diagram summarizing the topics in this review.
free piezoelectric materials were first reviewed by Damjanovic
et al.,96 and Shrout and Zhang comprehensively analyzed the
difference between KNN and PZT.18 Rodel et al. reviewed the
phase structure and electrical properties of KNN-based
materials by analyzing different processing techniques and
chemical modifications,17 and the related applications of lead-
free piezoelectrics have been recently summarized.120 Panda
reviewed the effects of additives on the electrical properties of
KNN-based materials.103 In 2009, Xiao et al. reviewed the
composition design and property modification of KNN- and
BNT-based ceramics by considering their recent publica-
tions.104 Li et al. introduced the developments of lead-free
piezoelectric materials in China, and their preparation and
electric properties were emphasized.266 More recently, the
phase structure (e.g., orthorhombic−tetragonal), property
enhancement approaches, and sintering processes as well as
some promising applications of KNN-based materials were
reviewed by Li et al.105 Finally, Priya et al. published a
monograph on lead-free piezoelectric materials in 2012.267 In
most reviews, the phase structure mainly refers to the
orthorhombic−tetragonal phase boundary or the KNN-based
materials are only reviewed as a minor part of a larger field or
from different viewpoints. In addition, there are few systematic
reviews on the developments of phase boundaries in
potassium−sodium−niobate-based materials. As mentioned
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above, the improved piezoelectricity of such a material should
be largely due to the construction of phase boundaries. As a
result, we focused our attention on the design and construction
of different phase boundaries (e.g., rhombohedral−orthorhom-
bic (R−O), orthorhombic−tetragonal (O−T), rhombohedral−
tetragonal (R−T), etc.) in potassium−sodium niobate
materials, the relationships between phase boundaries and
piezoelectricity are particularly emphasized, and some sugges-
tions have been addressed.
This review has been organized as shown in Figure 4. In the
first part, we give a general introduction to the background and
characterization methods of phase boundaries for elucidating
the phase structure−performance relationships. In the second
part, we focus on the design and construction of phase
boundaries in potassium−sodium niobate materials by chemical
modifications. Special emphasis is placed on the composition-
induced phase boundaries by analyzing the chemical
modifications in detail, and dopant engineering is also
mentioned. It is worth noting that we observed the largest
piezoelectricity ever reported by developing new phase
boundaries. In addition, supporting tools for further enhancing
piezoelectricity are also discussed in this review. In the third
part, we illuminate the relationships between phase boundaries
and piezoelectric activity, discuss some existing challenges,
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Figure 5. Intrinsic difference between (a) polymorphic phase transition (PPT) and (b) morphotropic phase boundary (MPB)17,200
Figure 6. Phase transition behavior of K0.48Na0.52Nb0.98Sb0.02O3 ceramics.
suggest possible methods for further improving piezoelectricity,
and provide some conclusions.
2. BACKGROUND OF PHASE BOUNDARIES
The modification of phase boundaries is a powerful tool for the
promotion of electrical properties of piezoelectric materials, i.e.,
the involved phase boundaries and their corresponding types
are largely responsible for the enhancement in piezoelectric
activity, regardless of whether a material is lead based or lead
free (refs 4, 5, 11, 16−19, 35, 70, 76, 96−120, and 286−315). A
number of experimental (refs 70, 287−298, 300, 301, 304, 305,
307, 309, 311, and 312) and theoretical methods (refs 20, 299,
301, 303, 306, 308, 310, and 313−315) have been used to
investigate the relationships between phase boundaries and the
piezoelectric activity of a material. It is generally accepted that a
high degree of alignments of ferroelectric dipoles can be driven
by a large amount of thermodynamically equivalent states
under a driving electric field during the poling process, easily
generating enhanced electrical properties.70,286−311 The con-
struction of morphotropic phase boundaries (MPB) in PZT is
considered a classic case in the field of piezoelectric
materials,286,289,293,305 wherein the crystal structure changes
abruptly and the piezoelectricity is maximized for compositions
at MPBs.286,289,293,305 For example, enhanced piezoelectric
activity was observed in PZT materials with a Zr/Ti ratio of
52:48 owing to the structural changes going from tetragonal to
rhombohedral via an intermediary monoclinic phase;292 this
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kind of phase boundary is thought to be an MPB,286 which is
only dependent on the compositions and independent of the
measurement temperatures, as shown in Figure 5b. However,
the phase boundaries (e.g., R−O and O−T) in KNN-based
materials were considered as the intrinsic characteristics of
“polymorphic phase transition (PPT)”,120,131 and their
electrical properties are very sensitive to not only the
compositions but also the temperatures (see Figure 5a).
According to advances in KNN materials, there are three
kinds of existing phase transitions (Figure 6), corresponding to
the rhombohedral−orthorhombic phase transition temperature
(TR−O), the orthorhombic−tetragonal phase transition temper-
ature (TO−T), and the rhombohedral−tetragonal phase
transition temperature (TR−T).17,18 Figure 6 shows the phase
transition behavior of K0.48Na0.52Nb0.98Sb0.02O3 ceramics,
measured at −150−550 °C and f = 10 kHz. One can see that
TR−O, TO−T, and TC are clearly shown according to the
temperature dependence of the corresponding dielectric peaks.
At room temperature, the R−O or O−T phase boundary could
be formed in KNN by shifting TR−O or TO−T to room
temperature using additives such as LiNbO3,101,160,161,166−178
Li(Ta/Sb)O3,102,133,163−165,182−203 Li(Ta−Sb)-
O3,132,151,156,157,204,206−214 (Bi0.5A0.5)TiO3 (A = Na+, K+,
Li+),215−218 BiBO3 (B = Al3+, Fe3+, Sc3+),225,230,252 SrZrO3,138
Sb5+,251 BaZrO3,397 Ta5+,254 etc. In contrast, the phase
boundary corresponding to R−O or O−T possesses the PPT
characteristic,97,155,251,264,265 depending on not only the
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Figure 7. d33 vs TC of (a) lead-based and (b) lead-free materials, derived from a number of publications.4,5,16−19,35,50,59,68,97,101,102,106,120,315−339
compositions but also the temperatures, as shown in Figure 5a.
Such a phase boundary is obviously different from that of PZT
(see Figure 5b). Regardless of the presence of MPB or PPT
characteristics, the polarization of a piezomaterial can be more
easily rotated among different symmetries when the composi-
tions are located at the phase boundaries, inducing an
enhancement in dielectric and piezoelectric properties.
However, recent advances indicate that there is a limited
improvement in the d33 values for KNN materials with O−T or
R−O phase boundaries,90−105,250−252 which is also inferior to
most PZT ceramics5 or even textured KNN.12 As a result, the
formation of R−T boundaries that are similar to PZT may
become necessary to further enhance the piezoelectric activity
of KNN, because the easy rotations of polarization axes can be
induced in compositions near such a phase boun-
dary.11,35,70,76,106−117 In addition, we recently confirmed this
assumption in potassium−sodium niobate piezoceramics by
experimental methods,106−116 and a larger d33 value has been
attained by constructing R−T phase boundaries.106−112 If the
R−T phase boundary of KNN is expected to form, it is
necessary to concurrently move their TR−O and TO−T values
close to room temperature by choosing two or more
additives, 1 0 6 − 1 1 6 , 2 5 5 − 2 6 3 such as Ta and Sb and
Bi0.5(Na0.82K0.18)0.5ZrO3,106 Sb and Bi0.5(Na0.82K0.18)0.5ZrO3,107
BaZrO3 and Bi0.5Na0.5TiO3,255 Sb and BaZrO3,256 Sb and
LiTaO3 and BaZrO3,257 LiSbO3 and BaZrO3,258 Sb and
Bi0.5Na0.5TiO3,259 Sb and (Bi,Na,K,Li)ZrO3,260
Bi0.5(Na0.7K0.2Li0.1)0.5ZrO3 and B0.5Na0.5TiO3,261 etc. As a result,
it is possible to develop high-performance KNN-based
materials by the application of new ideas.
The phase boundaries of a material can be driven by its
chemical composition or other factors (refs 4, 10, 35, 50, 59, 68,
97, 101, 102, 106, and 316−340) that determine the electrical
properties. Figure 7a and 7b shows the d33 vs TC of lead-based
(e.g., PZT, 4,5,316 Pb(Ni 1/3 Nb 2/3 )O 3 −PbTiO 3 (PNN−
PbTiO3),317−321 BiScO3−PbTiO3 (BSPT),322−332 and relaxor-
PbTiO3333−340) and lead-free (e.g.,
BaTiO 3 , 35−38,40−43,45,50,53,59,84 Bi 0.5 Na 0.5 TiO 3 , 63−73 and
(K,Na)NbO390−265) materials with compositions at the phase
boundaries, wherein all data were derived from the references.
A giant d33 value was observed in PNN-based and relaxor PT
single crystals with an MPB,317−321,333−340 while PZT-based
materials possess a wide d33 distribution,4,5,316 which is sensitive
to the doping elements, as shown in Figure 7a. Figure 7b
displays the d33 and TC values of BaTiO3-, Bi0.5Na0.5TiO3-, and
K0.50Na0.50NbO3-based lead-free ceramics with different phase
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boundaries (e.g., R−O, R−T, or O−T). Although a larger d33
can usually be realized in BaTiO3-based materials, a low TC is a
fatal shortcoming for high-temperature practical applica-
tions.35−38,40−43,45,50,53,59,84 However, such materials are
suitable to prepare actuators with usage temperatures below
100 ◦C. Similar to BaTiO3-based materials, the low “depoling
temperature” hinders the practical applications of
Bi0.5Na0.5TiO3-based materials,63−73 and a large strain com-
parable or even superior to PZT has been developed by Rödel
and Jo et al.66−68,73−77 More interestingly, we can see from
Figure 7b that KNN-based materials have wider d33 and TC
distributions (e.g., d33 = 171−490 pC/N, TC = 178−475 °C)
(refs 12, 17, 97, 101, 102, 104, 106−118, 166, 277, 284, and
285), which is determined by the phase boundary types and the
composition itself. In particular, we achieved a breakthrough in
the piezoelectricity of KNN-based ceramics by forming new R−
T phase boundaries.106−118 As a result, the construction of new
phase boundaries has become an efficient way to further
enhance the piezoelectricity of KNN materials, narrowing the
gap between lead-free and lead-based materials.
3. CHARACTERIZATION TOOLS OF PHASE
BOUNDARIES
Although the phase boundary has some incomparable
advantages, it is very difficult to know the actual phase
compositions and types of phase boundaries in a material.
Researchers have invested much effort in exploring the origin of
ultrahigh piezoelectricity in lead-based perovskite oxides with
MPBs by analyzing the phase constituents using experimental
and theoretical methods.65,287,298,323,341−391 Previously, it was
thought that 14 possible equivalent polarization vectors
determine the ultrahigh piezoelectric activity in MPB lead-
based materials.341 However, it was observed by means of high-
resolution X-ray powder diffraction measurements that
intermediate phases may coexist in the R−T phase boundary
of PZT,293,342,343,347 and an intermediate phase induces an
ultrahigh piezoelectricity. In particular, the monoclinic (M)
phase, as an intermediate phase of MPB, is considered to
effectively enhance the piezoelectricity of PZT.342 Since an M
phase was found in MPB-PZT,343 much attention has been
given to the determination of its phase compositions. Some
powerful tools can identify the existence of the intermediate
phases and thus explain the physical origin of enhanced
piezoelectricity, including high-resolution synchrotron X-ray
powder diffraction,293,298,342,344 neutron diffraction,359,360 spec-
troscopic techniques (i.e., Raman346,347,367−369 and infrared
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spectroscopies369,370), dielectric measurements,350 transmission
electron microscopy (TEM),361−366 theoretical studies,354,355
and Rietveld studies.376 In addition, two or more methods are
often used together to clarify the phase compositions near the
phase boundary regions of a material.371−375 In this section, we
briefly introduce the methods of characterization of the phase
compositions in KNN-based materials.
3.1. High-Resolution Synchrotron X-ray
Diffraction298,342,343,356−358
Structural information on lead-based piezoelectrics with MPBs
can be obtained by high-resolution synchrotron X-ray
diffraction.293,298,342,344,356−358 For example, Noheda et al.342
found that a monoclinic phase bridges tetragonal and
rhombohedral regions of PbZr0.52Ti0.48O3 using high-resolution
synchrotron X-ray powder diffraction measurements. In 2000,
Noheda et al.345 also established the stability region of three
phases (e.g., monoclinic, tetragonal, and rhombohedral phases)
in PbZr1−xTixO3 (0.42 ≤ x ≤ 0.52) according to data from
high-resolution synchrotron X-ray powder diffraction measure-
ments. These results indicate that PbZr1−xTixO3 (0.46 ≤ x ≤
0.51) ceramics possess a stable monoclinic phase when
measured at 20 K, the phase composition region becomes
narrower and narrower with increasing temperatures, and the
role of such a monoclinic phase in the ultrahigh piezoelectricity
of the materials was especially emphasized.293 In addition, this
method could also be used to detect the phase compositions of
other material systems.298,358 An orthorhombic phase in
PbZn1−xTixO3 and Pb(Zn1/3Nb2/3)O3−PbTiO3 systems was
identified by high-resolution synchrotron X-ray diffraction,298
and a monoclinic phase (Cm) of 0.65Pb(Mg1/3Nb2/3)O3−
0.35PbTiO3 was also confirmed.358
3.2. Neutron Diffraction359,360
Neutron diffraction allows the atomic and/or magnetic
structure of a material to be determined by neutron scattering,
and this technique has been used to evaluate the symmetry of a
material.359,360 For example, neutron diffraction methods can
identify the symmetry of Pb(Zn1/3Nb2/3)O3−9%PbTiO3 with
an MPB, showing that a new polarization rotation line Mc#
(the orthorhombic−monoclinic line) coexists with rhombohe-
dral and tetragonal phases.359 In addition, in situ neutron
diffraction experiments show that the varied coherence lengths
of polar nanoregions and internal stresses induced by domain
switching are responsible for different d33 values in textured and
polycrystalline 0.93Bi0.5Na0.5TiO3−0.07BaTiO3 ceramics.360
3.3. Transmission Electron Microscopy268,270,378
In 1931, Max Knoll and Ernst Ruska invented the first
transmission electron microscope (TEM), allowing the
structural information on ferroelectric materials to be directly
characterized.268,361−366 For example, both orthorhombic−
orthorhombic and paraelectric−ferroelectric phase transitions
in SrBi4Ti4O15 have been directly observed by TEM.363 Randall
et al.364 identified the differences between domain structure and
symmetry of (1−x)BiScO3−xPbTiO3 materials using TEM,
clearly showing the domain structures with R and T mixed
phases. In addition, the domain structure evolutions under an
applied electric field were characterized in situ in (Bi1/2Na1/2)-
TiO3−BaTiO3−(K0.5Na0.5)NbO3 ceramics using TEM.365 This
result indicates that the domain structure cannot be clearly
observed when an electric field is retrieved, while a lamellar
domain structure can be driven by an alternating electric field,
graphically showing the involvement of electric field-induced
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phase transitions from a nonpolar to a ferroelectric state.365 Yao
et al.366 reported that the ferroelectric domains and local
structures of Bi0.5Na0.5TiO3−BaTiO3 single crystals could be
identified by TEM, the size of polar nanoregions were refined,
and the tetragonal phase volume fraction was shown to increase
as the BT content increased, indicating that both polarization
rotation and polarization extension lead to large electric-field-
induced strains in materials with MPBs.366 Recently, Zuo et
al.268 discussed the origin of the high piezoelectric activity in
(Na0.52K0.48−x)(Nb0.92−xSb0.08)O3−xLiTaO3 ceramics by char-
acterization of the domain evolutions using TEM, indicating
that the nanodomain morphologies are responsible for their
enhanced piezoelectricity.
In the past, the relationships between grain size and domain
of ferroelectric materials were extensively investigated using
TEM in order to understand the size effect on their electrical
properties.377−383 It is well known that the domain size of
ferroelectric materials is closely related to the corresponding
grain size, as shown here.382,383
Domain Size ≈ (Grain Size)m (1)
According to eq 1, the grain size of the samples used for
TEM observation can strongly affect their domain size,382 that
is, the prepared samples are in agreement with the bulk domain
structures. As a result, it becomes critical to accurately
characterize the domains to evaluate the underlying physical
mechanisms. To attain useful information about material
structure and properties, TEM becomes an indispensable
tool. However, the size effects of ferroelectric materials
presumably play a part in the TEM observations of domains,
since the TEM samples are quite thin. Therefore, the sample
preparation technique is very important for TEM analysis in
order to gain real insight into a material’s structure.384 It is
usually very challenging to prepare a suitable sample of
polycrystalline ceramics for TEM since some additional cracks
and artifacts may be introduced during the sample prepara-
tion.384 In addition to the TEM observation of domains, other
tools (scanning electron microscopy,269 piezoresponse force
microscopy,270,271 etc.) should also be used to further confirm
the domain structure and to avoid artificial information. As a
result, TEM can directly characterize domain structure and
morphologies, and the size effects should be given special
attention in the observation of domains.
3.4. Spectroscopic Techniques
Spectroscopy is used to investigate the interactions between a
material and radiated energy;342,347,367−370 thereby, the phase
transitions of a material can be analyzed by spectroscopic
techniques including Raman and infrared spectroscopies.367−370
3.4.1. Raman Spectroscopy. Raman spectroscopy is used
to characterize vibrational, rotational, and other low-frequency
modes in a material and can also identify the phase structure of
a material.346,347 In 2000, Souza Filho et al. confirmed the MPB
consisting of tetragonal and monoclinic phases 346 in
PbZr0.52Ti0.48O3 by Raman spectroscopy with the frequency
and temperature of lattice modes.347
Confocal Raman microscopy can allow high-resolution
chemical mapping of 2D or 3D materials. Recently, confocal
Raman microscopy (CRM) coupled with atomic force
microscopy has been used to observe the domains of KNN-
based materials.272,273 For example, Rubio-Marcos et al.
identified the spatially resolved structure of the ferroelectric
domains in (K,Na)NbO3-based ceramics by confocal Raman
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Figure 8. Possible chemical modifications of (K,Na)+ and Nb5+ sites in (K,Na)NbO3.
microscopy, where the characteristics of domain walls and
structure−piezoelectricity correlation were clearly addressed.272
3.4.2. Infrared Spectroscopy. Infrared spectroscopy uses
radiation from the infrared region of the electromagnetic
spectrum, covering a range of techniques based on absorption
spectroscopy. It is well known that the onset of ferroelectric
states can cause a change of infrared vibrational frequencies
owing to its temperature-dependent phase transitions and thus
can be used to characterize their phase transitions.369,370 For
example, Araujo et al.369 showed that monoclinic → tetragonal
phase transitions in PbZr0.51Ti0.49O3 occur at 237 K by infrared
spectroscopy, confirming this technique as a useful tool to
analyze phase transitions. The monoclinic → tetragonal phase
transitions in PbZr0.50Ti0.50O3 can be confirmed by infrared
spectroscopy with different measurement temperatures, and the
obvious differences in higher frequency ν1-(Ti−O) and ν1-(Zr−
O) modes can show the structural changes in monoclinic →
tetragonal phases.370
3.5. Theoretical Methods274−276,287,355,364,365,385−391
Theoretical methods rely on the creation of hypothetical
models of materials. Such methods can predict the underlying
physical mechanisms of enhanced electrical properties well,
effectively supporting experimental results. In the past,
theoretical methods have also been used to explain the origin
of ultrahigh piezoelectricity of lead-based materials with an
MPB, such as a first-principle study by Fu and Cohen,287 and
higher-order Devonshire theory studies by Vanderbilt and
Cohen.355 Fu et al. also reported that the large piezoelectricity
in BaTiO3 is driven by the polarization rotation induced by an
external electric field using a first-principles study.287 In
addition, some theoretical methods were also used to
investigate single-phase KNN materials.274−276 For example,
Zhu et al. indicated a combination of negative spherical-
aberration imaging using first-principles calculations and
studied the atomic details across 60°/120° domain walls in
(K0.46Na0.54)NbO3, providing an atomic basis for further
investigation of the polarization mechanism.274 However, few
attempts have been made to predict the phase boundaries in
KNN materials.
2565
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Although theoretical methods can further guide experimental
studies, there are also limitations inherent in some methods.
Most theoretical methods are only capable of modeling realistic
systems,385,386 and the final results are also strongly dependent
on different simulated methods.387−389 For example, simu-
lations of the domain structures of ultrathin ferroelectric films
have mainly focused on conventional perovskite ferroelectrics
(e.g., BaTiO3,390 PbTiO3,391 etc.). In these studies, only a few
simple factors (e.g., boundary conditions, external electrical,
and mechanical loads) were considered,390,391 while treatment
of complicated situations and the detailed physics of the surface
and interface (i.e., octahedral rotation, magnetic ordering, other
degrees of freedom) was seriously flawed. In addition,
theoretical methods have so far been unable to model the
true dynamics of the domain structures of ultrathin ferroelectric
films.385 As a result, satisfactory simulation of broad and
complicated systems will require further development of
computational methods,385 and special attention should be
given to the limitations of theoretical methods on the whole.
3.6. Combined Tools323,371−375
It is usually difficult to identify the phase compositions of a
material using only one tool; thus, multiple techniques should
be used to determine the actual phase compositions.323,371−375
In the past, combined tools have been used to identify the
phase structures of lead-based and lead-free materials.323,372−375
For example, both variable-temperature transmission electron
microscopy and dielectric measurements were used to
characterize the phase compositions of (1−x)BiScO3-xPbTiO3
single crystals in which x = 0.64.323 Schonau et al. studied the
phase compositions and microstructural information on
Pb(Zr1−xTix)O3 (0.40 ⩽ x ⩽ 0.475 and x = 0.55) materials
using three different tools (e.g., high-resolution synchrotron X-
ray diffraction, transmission electron microscopy, and electron
paramagnetic resonance) and found that a monoclinic phase is
correlated to a miniaturization of its average domain
structure.371 The phase compositions of (1−x)Pb(Ni1/3Nb2/3)-
O3−xPbTiO3 (x = 0.28−0.42) solid solutions were confirmed
by using both high-resolution synchrotron radiation X-ray
diffraction and dielectric measurement, indicating that the
intermediate monoclinic phase exists between rhombohedral
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and tetragonal phases.372 Singh et al. investigated the
temperature-dependent phase structure in monoclinic Pb-
(Zr0.525Ti0.475)O3 powders by Rietveld analysis of high-
resolution synchrotron powder X-ray diffraction data in
combination with its dielectric constant and planar electro-
mechanical coupling coefficient.373 These powders, with a
tetragonal phase, possess better piezoelectric activity than those
with a monoclinic phase because of an anomalous softening of
the elastic modulus.373 Fu et al. studied the origin of enhanced
piezoelectricity in (Na,K)(Nb,Sb)O3−LiTaO3−BaZrO3 ce-
ramics by combined tools consisting of high-resolution
synchrotron X-ray data and dielectric measurements, showing
that an intermediate phase between R and T leads to a larger
piezoelectricity.374 Maurya et al. addressed the origin of high
piezoelectricity in 0.93(Na0.5Bi0.5)TiO3−0.07BaTiO3 with an
MPB by comparative analyses of high-resolution transmission
electron microscopy and neutron diffraction, confirming that a
pathway for polarization reorientation induced by an
intermediate monoclinic phase with nanotwins results in
enhanced piezoelectricity.375 As a result, multiple characteration
methods can compensate for the shortcomings of a single
method, thereby more accurately showing the phase
compositions of a material.
4. TYPE AND CONSTRUCTION OF PHASE
BOUNDARIES
It is widely accepted that the piezoelectric activity of a material
can be promoted by forming phase boundaries by chemical
modification (e.g., ion substitutions, binary or ternary solid
solutions, etc.).11,35,70,76,286−311 As far as KNN-based materials
are concerned, three kinds of phase boundaries (i.e., O−T, R−
O, and R−T) can be driven by doping with additives (refs
96−119, 131, 132, 136, 151, 152, 157, 161, 166, 169, 186−188,
and 392−405), resulting in enhanced piezoelectricity.
Among these methods, chemical modifications are often used
to tailor the phase compositions in the phase boundary regions
of KNN materials. To graphically show the chemical
modifications of KNN materials, we depict the chemical
modifications of (K,Na)+ and Nb5+ sites in (K,Na)NbO3 in the
Periodic Table (Figure 8). The colored boxes represent
different chemical modifications of (K,Na)NbO3. Usually
monovalent cations (e.g., Li+101,162,166−173,392−394 and Ag+ )
are able to easily substitute the (K,Na) site, and the Nb5+ site is
often replaced by pentavalent cations (e.g.,
Ta5+ 102,162,163,193−203 and Sb5+ 182−190) because of their
identical valence and similar ionic radii. In addition, ABO3
can be constructed by combining (Mg, Ca, Sr, Ba, Pb) and (Ti,
Zr, Hf, Sn) with Bi and (Y, Fe, Sc, Ga, Al, In),229−242 and this
ABO3 can be used to modify the KNN materials. The KNN-
based materials are also modified by doping elements (e.g., V,
Mn, Co, Ni, Cu, Zn, B, La, Ce, Pr, Nd, Dy, Yb, etc.) in the form
of oxides, and electrical properties can be controlled by
tailoring the defect types. Recently, special ABO3 additives
containing Bi3+ and Zr4+ have been found to greatly promote
the piezoelectric activity of KNN-based materials by the
construction of R−T phase boundaries,106−113 where Bi3+ and
Zr4+ can, respectively, lower TO−T and increase TR−O and Sb5+
ions can further compact the O phase zone.106−113 By the
thought of phase boundary, a large d33 of >400 pC/N was
attained in KNN-based ceramics by doping of Bi0.5M0.5ZrO3
(M = Na+ and/or Li+ and/or K+ and/or Ag+),106−113 and the
different d33 values originate from the variance in TR−T.277
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Review
In this section we mainly review the development of different
types and constructions of phase boundaries in KNN materials,
and some advice is provided for attaining piezoelectric activity
comparable to that of PZT. In addition, the detailed discussions
on how to construct phase boundaries by chemical
modifications are summarized here.
4.1. Orthorhombic−Tetragonal Phase Boundaries
The O−T phase boundary has become the most familiar one
since a large breakthrough was achieved in KNN-based
materials.12,101 The formation of the O−T phase boundary is
one of the mosty hotly contested goals of research into KNN-
based materials (refs 101, 102, 132, 151−157, 159−168,
170−178, 182−197, 199−218, 220, 221, 224, and 229−247).
In 2004, the original breakthrough in its d33 value was achieved
by varying O−T phase coexistence to or near room
temperature using Li, Ta, and Sb.12 For example, a high d33
value of ∼416 pC/N was induced in KNN-based textured
ceramics due to coexistence of O and T phases at room
temperature as well as the use of a new preparation technique
(e.g., RTGG),12 while at the same time LiNbO3- or LiTaO3-
modified KNN ceramics have attained enhanced piezoelectric
activity by construction of the same phase boundary using
conventional solid-state methods.101,102 These original works
have greatly increased worldwide research interest in lead-free
piezoelectrics, and thus, scientists have devoted much energy
into further promotion of the piezoelectric activity by
constructing O−T phase boundaries (refs 101, 102, 132,
151−157, 159−168, 170−178, 182−197, 199−218, 220, 221,
224, and 229−247). In the past, a number of successful
attempts were made to construct O−T phase boundaries in
KNN-based ceramics in order to induce enhancement of its
piezoelectric activity, including ion substitutions (e.g., using
Li+,101,160,161,166−181 Li+/Sb5+,182−192 Li+/Ta5+,102,162,163,193−203
Li+/Sb5+ /Ta5+,12,156,204−214 etc.), solid solutions with other
ABO 3 -type perovskites 215−228 or ABO 3 multicompo-
nents,229−243 variation of the K/Na ratio,156,186,244−247 new
preparation techniques,109,125,165,166,175−177,190,196,210,245 etc. In
this section we focus on reviewing the methods of construction
of O−T phase boundaries.
4.1.1. Li+ Substitution. Ion substitution has become a
popular way to promote the piezoelectric properties of KNN-
based materials by the construction of O−T phase boundaries.
It is now well known that Li+, Sb5+, and Ta5+ are the leading
doping elements,12,102,156,160−163,166−214 which are able to
quickly shift the O−T phase boundary at or near room
temperature, resulting in an enhanced d33 value owing to the
facilitated polarization rotations induced by the structural
instability.11,35,70,76 However, doping with Li+ is first used to
improve the piezoelectric activity of KNN materi-
als.101,166−173,394 Table 1 displays the piezoelectric activity of
Li+-doped KNN materials.101,162,166−173 There are a number of
advantages of introducing Li+ into KNN materials. First, adding
Li+ can increase TC, decrease TO−T, and slightly affect TR−O
values of KNN ceramics;174 thereby the O−T phase boundary
can be formed, improving the piezoelectric activity of the
material.101 Second, the doping with Li+ can also decrease the
sintering temperatures and improve the density of KNN
materials.101,166−173 It was shown that d33 values of 188−324
pC/N could be obtained by doping 6−8 mol % Li+ into KNN
ceramics due to the formed O−T phase boundary,101,166−173
and the actual Li+ content at maximum d33 also depends on the
different processing methods.101,166−173 It is also worth noting
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Table 1. Piezoelectric Activity of Li+-Modified KNN is sensitive to not only the phase boundary and but also the
Materials with O−T Phase Boundaries compositions; thus, further investigation is necessary.
4.1.2. Li+ and Sb5+ Substitution. Many studies have
d33 (pC/ Tc
material system N) kp (°C) ref involved systematic investigation of the piezoelectric properties
of Li+- and Sb5+-codoped KNN materials, the general idea
K0.47Na0.47Li0.06NbO3 235 0.38 475 Guo101
being to shift TO−T to (or near to) room temperature by
(K,Na,Li)NbO3 324 0.54 Li and Wang166
modifying the Li+ and Sb5+ content.182−192 In fact, Li+ plays a
0.94K0.49Na0.51NbO3− 246 0.42 467 Li167
0.06LiNbO3 large part in the decreased TO−T of KNN,101,162,166−173,392−394
0.92Na0.535K0.48NbO3− 280 0.48 475 Li and Wang168 and Sb5+ can simultaneously decrease TO−T and increase
0.08LiNbO3 TR−O,106−110,251,392 as shown in Table 2. As a result, doping
0.93K0.5Na0.5NbO3− 274 Du169
0.07LiNbO3
Table 2. Effects of Li+, Sb5+, and Ta5+ on Both TO−T and
(K0.5Na0.5)0.935Li0.065NbO3 188 471 Wongsaenmai170
TR−O of a Pure KNN Ceramic101,251,254
(K0.5Na0.5)0.94Li0.06NbO3 235 0.42 Kakimoto171
0.94K0.5Na0.5NbO3− 215 0.41 450 Du172 1 mol % Li+ Sb5+ Ta5+
0.06LiNbO3
TO−T (°C) −30 −10.7 −4.0
0.93K0.5Na0.5NbO3− 240 0.35 Song173
0.07LiNbO3 TR−O (°C) +14.8 +2.3

with Li+ and Sb5+ can further move a material’s TO−T close to
that Guo et al. achieved the first breakthrough in d33 values of
room temperature. As shown in Table 3, codoping with Li+ and
Li+-modified KNN ceramics prepared by the conventional
solid-state method,101 and an enhanced d33 value of ∼235 pC/
N was reached when the TO−T was tuned to near room Table 3. Piezoelectric Activity of Li+- and Sb5+-Modified
temperature, which is one-third as much as a pure KNN KNN Ceramics with O−T Phase Boundaries
ceramic.101,166−174 However, such a d33 value is still inferior to d33 (pC/ Tc
those of most PZT ceramics,4,5 and thus, other attempts must material system N) kp (°C) ref
be made to further increase its d33 value.169,173,175−181 For 0.948(K0.5Na0.5)NbO3− 265 Zhang182
example, Song et al. increased the d33 values of 0.93KNN− 0.052LiSbO3
0.07LN ceramics from ∼195 to 240 pC/N by increasing their 0.95(K0.48Na0.52)NbO3−0.05LiSbO3 262 0.46 373 Wu183
grain sizes using two-step sintering methods (sintering at 1030 0.94(K0.5Na0.5)NbO3−0.06LiSbO3 212 0.46 358 Lin184
°C and subsequent annealing at 1050 °C).173 Du et al. studied 0.95K0.49Na0.51NbO3−0.05LiSbO3 256 0.43 340 Li185
the effects of both sintering temperatures and poling conditions 0.95(K0.40Na0.60)NbO3−0.05LiSbO3 280 0.49 364 Wu186
(e.g., poling temperature, poling electric field, etc.) on the 0.95(K0.42Na0.58)NbO3−0.05LiSbO3 270 0.47 364 Wu187
piezoelectric activity of KNN−LiNbO3 ceramics and found that (Na0.5K0.5)1−x(LiSb)xNb1−xO3 260 0.50 390 Zang188
two methods can further optimize their piezoelectric proper- 0.95K0.5Na0.5NbO3−0.05LiSLbO3 215 0.42 386 Palei189
ties.169,175,176 Zhao et al.177 reported that high piezoelectricity (Na0.474K0.474Li0.052)(Nb0.948Sb0.052) 242 0.42 Zhao190
O3
(d33 ≈ 314 pC/N) can be attained in Li+-modified KNN (Na0.5K0.5)0.945Li0.055Nb0.96Sb0.04O3 240 Li191
ceramics by adding excess Na+ (∼2.9%) and choosing optimum
sintering temperatures (∼1060 °C). Li and Wang et al.178
reported that a high converse piezoelectric coefficient (d33* ≈ Sb5+ can enhance the d33 values (∼210−280 pC/N) of KNN
538 pm/V) compared to PZT could be observed in Li+- materials.182−191 We can see from Table 3 that two different Li+
modified KNN ceramics when a low applied electric field (∼1 and Sb5+ doping methods were used to modify KNN, including
kV/mm) was used. In addition, they also developed a new LiSbO3182−190 and Li+/Sb5+.191 The O−T phase coexistence of
poling method to further improve the piezoelectricity by aging KNN−LiSbO 3 ceramics can be effected with LiSbO 3
and repoling-induced enhancement of the piezoelectricity (d33 compositions at 5−6%, leading to d33 values of 210−280 pC/
≈ 324 pC/N) in such a ceramic owing to both the defect N.182−190 For example, Zhang et al.182 reported that an
migration and the rotation of the spontaneous polarization.166 enhanced d33 value of ∼265 pC/N was observed in
This is considered the second major breakthrough with regard 0.948(K0.5Na0.5)NbO3−0.052LiSbO3 ceramics due to the
to the d33 values of Li-modified KNN ceramics. The Bridgman formation of O−T phase boundaries, showing the strong
method was used to prepare (001)-oriented 0.95KNN−0.05LN temperature dependence of d33. In the development of KNN-
single crystals, leading to a high d33 of 405 pC/N and a large based materials, Sb5+ plays a large part in the construction of
thickness electromechanical coupling factor (kt) of 61%,181 phase boundaries, especially for R−T.106−110 In addition, we
which can be regarded as the third breakthrough for this confirmed that adding Sb5+ can decrease the TR−O and TO−T
material system. It is well known that the TO−T in KNN has values of KNN materials to room temperature (see Figure
both advantages and disadvantages, i.e., a large d33 vs a poor 9),392 and thus, Sb5+ and other additives can result in a high
temperature stability.182 Higashide et al.,160 Hollenstein et piezoelectricity by forming R−T phase boundaries.106,107 As a
al.,161 and Zhai et al.245 investigated the temperature stability of result, Sb5+ plays a very important role in the construction of
the piezoelectric properties of Li+-modified KNN ceramics, and phase boundaries and the enhancement of piezoelectric activity
a poor temperature stability was demonstrated when the of KNN-based materials.
compositions were at the O−T phase boundary zone. However, 4.1.3. Li+ and Ta5+ Substitution. For KNN materials,
an opposite result has been found by Li and Wang et al., and adding both Li+ and Ta5+ has advantages similar to those of Li+
there is a slight variance in field-induced strain of Li+-doped and Sb5+,102,162,163,193−203 that is, the decreased TO−T near
KNN from room temperature to 175 °C.278 The authors room temperature can lead to a high piezoelectric activ-
wondered whether the temperature stability of KNN materials ity.102,162,163,193−203 However, we still find some differences
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Figure 9. Phase diagram and d33 values of (K0.48Na0.52)(Nb1−xSbx)O3
ceramics.392
between the two, namely, the addition of Li+ and Ta5+ more
slowly decreases its TC value with respect to those modified by
Li+ and Sb5+ (see Table 2).196,197,251,254 As a result, doping with
both Li+ and Ta5+ is another effective way to promote the
piezoelectric activity of KNN materials without seriously
sacrificing its TC,196,197,254 as shown in Table 4. Guo et al.102
first reported that KNN−LiTaO3 ceramics possess the
enhanced piezoelectric properties of d33 ≈ 200 pC/N and kp
≈ 0.36 when the compositions are located at the O−T phase
boundary. In addition, some references also show that a high
Ta5+ content leads to a high d33 in KNN-based systems.193,195
For example, a d33 value of >250 pC/N was observed in KNN-
based ceramics by doping a Ta content of ≥15%.193,195
However, production costs inevitably increase when doping
excess Ta5+ into KNN materials, limiting their large-scale
industrial applications. As a result, it is necessary to develop
methods to further promote the piezoelectricity of KNN
ceramics using a low Ta5+ content.196−198 For example, using
excess Li2O as a sintering aid and the formation of O−T phase
boundaries induces a high d33 of ∼250 pC/N in 0.95-
(Na0.5K0.5)NbO3−0.05LiTaO3,198 and a high d33 value (∼268
pC/N) in (K,Li)(Nb,Ta)O3 ceramics can also be attained by
both constructing the same phase boundary and introducing
excess Na+.202 Although the piezoelectric activity of KNN
ceramics could be enhanced by adding Li+ and Ta5+, the
addition of Ta5+ should be avoided as far as possible or be used
at low content levels with an eye toward practical applications.
4.1.4. Li+, Sb5+, and Ta5+ Substitution. Although Li+, Li+
and Ta5+ or Li+ and Sb5+ can improve the piezoelectric activity
of KNN materials by forming O−T phase bounda-
Table 4. Piezoelectric Activity of Li+- and Ta5+-Modified KNN Ceramics with O−T Phase Boundaries
material system d33 (pC/N)
0.93(K0.5Na0.5)NbO3−0.07LiTaO3 200
(K0.5−x/2Na0.5−x/2Lix)(Nb1−y,Tay)O3 190
(Li0.04Na0.48K0.48)(Nb0.80Ta0.20)O3 215
[(K0.458Na0.542)0.96Li0.04](Nb0.85Ta0.15)O3 298
[(K0.5Na0.5)0.97Li0.03](Nb0.8Ta0.2)O3 234
(K0.55Na0.45)0.965Li0.035Nb0.80Ta0.20O3 262
(Na0.535K0.485)0.926 Li0.074(Nb0.942Ta0.058)O3 276
[(Na0.535K0.480)0.942Li0.058](Nb0.94Ta0.06)O3 232
Li2O−0.95(Na0.5K0.5)NbO3−0.05LiTaO3 250
(K0.5Na0.5)0.96Li0.04(Nb0.775Ta0.225)O3 208
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Review
ries,101,102,162,163,166−173,182−203,392−394 the d33 values of the
materials are usually less than 300 pC/N. As a result, a major
goal is the discovery of KNN-based materials with higher d33
values. Among the range of chemical modifications, codoping
with Li+, Ta5+, and Sb5+ can cause rapid decreases of TO−T in
KNN materials (see Table 5),12,156,157,204−214 and finally the
O−T phase boundary near room temperature can be more
rapidly tuned by controlling the elemental contents. For
example, Satio et al.12 reported that a high d33 value of ∼416
pC/N can be achieved in Li+, Ta5+, and Sb5+ codoped KNN
textured ceramics. Although such a high d33 can be comparable
to those of PZT materials,12 the expensive RTGG methods
used seriously limit their practical applications. If a similar
material system with a high d33 can be prepared by
conventional solid-state methods, the pace of their practical
applications may be further accelerated. As a result, efforts have
focused on developing KNN ceramic systems containing Li+,
Ta5+, and Sb5+ by conventional solid-state methods, and d33
values of >300 pC/N can often be attained by controlling the
ratios of three elements (e.g., Li+, Ta5+, and Sb5+).156,157,204−210
As shown in Table 5, the composition-induced O−T phase
boundary is largely responsible for the enhanced piezo-
electricity of KNN-based ceramics.12,156,157,204−214 For exam-
ple, excellent piezoelectric properties (d33 ≈ 413 pC/N) were
observed when low Li+ (∼2%) and high Ta5+ (∼18%) contents
were doped into KNN-based ceramics,204 and (K0.52Na0.45)-
(Nb0.88Sb0.09)O3−0.03LiTaO3 ceramics also exhibit a high d33
value of ∼400 pC/N.205 However, these results show that their
d33 can be improved greatly by sacrificing the TC (≤230 °C)
values of KNN,204,205 as shown in Table 5. In addition, a high
Ta5+ content is still necessary to obtain a large d33 value in these
studies;157,204,207,211 otherwise, a lower d33 is often encoun-
tered.212,214 As a result, codoping with Li+, Ta5+, and
Sb5+12,156,204−208 frequently contributes to the enhancement
of piezoelectric activity of KNN ceramics with respect to those
doped by one or two of the three ele-
ments, 101,102,162,163,166−173,182−203,392−394 but high costs
(Ta5+) and low TC values may be two stubborn issues
impacting their practical application.
4.1.5. Addition of ABO3. Perovskite ABO3 materials are
often used to modify KNN in order to induce enhancement in
piezoelectric activity by favoring the formation of phase
boundaries,215−228 such as Bi0.5A0.5TiO3 (A = Na+,215,216
K + ,217 Li + 218 ), BTiO 3 (B = Ba 2+, 219 Sr2+ , 219 Ca 2+, 223
(Ba0.95Sr0.05)2+,224 [(Bi0.5Na0.5)0.94Ba0.06]2+,220 BiMO3 (M =
Sc3+,225 Al3+,226 Fe3+,227 Co3+ 228)), and others. Table 6 lists
the piezoelectric properties of ABO3-modified KNN ce-
ramics.215−228 Doping with ABO3 can effectively promote the
kp Tc (°C) ref
0.36 Guo102
0.46 310 Hollenstein162
0.43 Wang163
0.52 366 Chang193
0.51 358 Satio194
0.53 325 Zhang195
0.46 ∼450 Shen196
0.39 462 Zhao197
0.37 Kim198
0.48 320 Lin199
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Table 5. Piezoelectric Activity of Li-, Ta-, and Sb-Modified KNN Ceramics with O−T Phase Boundaries
material system d33 (pC/N) kp Tc (°C) ref
(K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3 416 0.61 253 Satio12
(K0.38Na0.58Li0.04)(Nb0.91,Ta0.05,Sb0.04)O3 306 0.48 Wu156
(K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 345 ∼249 Akdogan157
(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3 413 0.50 ∼225 Gao204
(K0.52Na0.48−x)(Nb1−x−ySby)O3−xLiTaO3 400 0.54 ∼230 Zuo205
(Na0.52K0.44Li0.04)Nb0.87Sb0.08Ta0.05O3 376 0.44 ∼270 Du206
(Na0.5K0.5)0.975Li0.025Nb0.76Sb0.06Ta0.18O3 352 0.47 ∼210 Du207
(Na0.52K0.4375)(Nb0.9075 Sb0.05)O3−0.0425LiTaO3 321 0.52 315 Fu208
(Na0.52K0.48−xLix)Nb1−x−ySbxTayO3 308 0.51 339 Ming209
(K0.4425Na0.52Li0.0375)(Nb0.8925Sb0.07Ta0.0375)O3 304 0.48 271 Pang210
Li0.04(Na0.54K0.46)0.96Nb0.81Ta0.15Sb0.04O3 293 0.46 340 Noh211
Li0.02(Na0.55K0.45)0.98(Nb0.77Ta0.18Sb0.05)O3 256 0.42 Yoo212
0.96(K0.48Na0.52)(Nb0.95Ta0.05)O3−0.04LiSbO3 250 0.45 348 Wu214

Table 6. Piezoelectric Properties of ABO3-Modified KNN formation of O−T phase boundaries by decreasing a material’s
Ceramics T O−T values, inducing enhanced piezoelectricity.215−224
Although ABO3-type additives can increase the d33 values of
d33
(pC/ Tc KNN-based mateials,215−228 the resulting values are still inferior
material system N) kp (°C) ref to those of KNN ceramics containing Li+, Ta5+, and
0.97(K0.5Na0.5)NbO3− 195 0.43 375 Zuo215 Sb5+,156,157,204−211 as shown in Tables 5 and 6. However, the
0.03(Bi0.5Na0.5)TiO3 low cost of ABO3 may make it a potential candidate for
0.975(K0.5Na0.5)NbO3− 256 0.48 373 Du216 practical applications.
0.025(Bi0.5Na0.5)TiO3
4.1.6. Addition of ABO3 Multicomponents. KNN
0.98(K0.5Na0.5)NbO3−0.02(Bi0.5K0.5) 251 0.49 376 Du217
TiO3 ceramics doped with ABO3 multicomponents usually possess
0.98(K0.5Na0.5)NbO3− 172 0.37 381 Jiang218 enhanced piezoelectric behavior (d33 = 220−305 pC/N)
0.02Li0.5Bi0.5TiO3 together with high TC values of >300 °C,229−242 as shown in
0.94(Na0.5K0.5)NbO3−0.06BaTiO3 150 0.34 279 Wang219 Table 7. Results show that doping with most ABO 3
0.95(Na0.5K0.5)NbO3−0.05SrTiO3 195 0.37 289 Wang219 multicomponents can shift a material’s TO−T to room
0.96(Na0.5K0.5)NbO3− 256 0.43 395 Chen220 temperature, resulting in the formation of O−T phase
0.04(Bi0.5Na0.5)0.94Ba0.06TiO3 boundaries. As indicated in Table 7, the ABO3 materials
(K0.5Na0.5)NbO3−Ba(Zr0.05Ti0.95) 234 0.49 318 Lin221 containing Bi3+ are often used to modify KNN-based ceramics,
O3−MnO2
K0.5Na0.5NbO3− 203 0.45 342 Lin222
such as BiFeO3,229−232 BiScO3,233−235 BiAlO3,241 etc. Among
CaTi0.9Zr0.1O3+MnO2 BiMeO3 (Me = Fe, Sc, Al, etc.) additives, doping with BiFeO3
0.95(Na0.5K0.5)NbO3−0.05CaTiO3 241 0.41 306 Park223 or BiScO3 greatly favors increases in d33, and d33 values of >250
0.97(Na0.5K0.5)NbO3− 136 0.21 Kim224 pC/N are often obtained in such ternary systems by formation
0.03(Ba0.95Sr0.05)TiO3 of O−T phase boundaries.229−231,233 The differences in
0.9825K0.5Na0.5NbO3−0.0175BiScO3 253 0.48 351 Du226 increases in d33 mainly originate from the velocity of shifting
0.99(Na0.5K0.5)NbO3−0.01BiAlO3 202 0.46 372 Zuo225 TO−T. For example, Jiang et al.229 investigated KNN−LiSbO3−
0.99K0.5Na0.5NbO3− 144 0.34 370 Zhang227 BiFeO3 ternary systems in order to shift the TO−T nearer to
0.01Bi0.8La0.2FeO3
room temperature, finding that low amounts of BiFeO3 (0.4
(1−x)(Na0.5K0.5)NbO3−xBiCoO3 165 0.40 370 Xiao228
(x = 0.01) mol %) increase the d33 values from ∼202 to 260 pC/N. As a
result, BiFeO3 as an ABO3 component can effectively enhance

Table 7. Piezoelectric Properties of KNN Ceramics with ABO3 Multicomponents

material system d33 (pC/N) kp Tc (°C) ref

0.996(0.95Na0.5K0.5NbO3−0.05LiSbO3)−0.004BiFeO3 260 0.52 365 Jiang229
0.95(0.995Na0.5K0.5NbO3−0.005BiFeO3)−0.05LiSbO3 257 0.52 365 Jiang230
0.996[(K0.458Na0.542)0.96Li0.04](Nb0.85Ta0.15)O3−0.004BiFeO3 261 0.58 345 Chao231
0.995Li0.03(Na0.53K0.48)0.97Nb0.8Ta0.2O3−0.005BiFeO3 238 0.47 300 Zhou232
0.995(0.95K0.5Na0.5NbO3−0.05LiSbO3)−0.005BiScO3 280 0.49 ∼340 Li233
0.992(0.95K0.5Na0.5NbO3−0.05LiSbO3)−0.008BiScO3 305 0.54 315 Jiang234
0.99(Na0.485K0.485Li0.03)NbO3−0.01BiScO3 225 0.38 402 Sun235
0.998[0.95(K0.5Na0.5)NbO3−0.05LiSbO3]−0.002BiFe0.8Co0.2O3 276 0.48 340 Zhao236
0.96(0.99K0.5Na0.5NbO3−0.01Bi0.5Na0.5TiO3)−0.04LiSbO3 250 0.29 339 Liu237
0.938Na0.5K0.5NbO3−0.002BiNiO3−0.06LiSbO3 240 0.44 360 Liu238
(Li,K,Na)(Nb,Sb)O3−LiSbO3−(Ba,Ca)(Ti,Zr)O3 237 0.49 335 Wu239
K0.5Na0.5NbO3−LiNbO3−BNKT 240 0.46 469 Chen240
0.998(0.948 K0.5Na0.5NbO3−0.052LiSbO3)−0.002BiAlO3 233 0.35 349 Liu241
0.996(K0.475Na0.475Li0.05)(Nb0.95Sb0.05)O3−0.004Bi(Ni0.5Ti0.5)O3 253 0.52 ∼350 Yang242

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the piezoelectric activity of KNN−LiSbO3 ceramics by forming
O−T phase boundaries at or near room temperature. However,
doping with BiScO3 has different effects on the piezoelectric
activity of KNN-based ceramics.233,234 For example, a d33 value
of ∼305 pC/N was shown in K0.5Na0.5NbO3−LiSbO3−BiScO3
ternary systems with pure tetragonal structures; the authors
reasoned that the phase boundary cannot play an important
role in the improved piezoelectric properties.234 However, we
found that the addition of BiScO3 results in increased TR−O
values and decreased TO−T values of KNN;108,109 thus, the new
R−T phase boundary could be finally formed at room
temperature. In addition, the dielectric constant of this material
gradually increases with decreasing measurement temper-
atures,234 suggesting the involvement of phase boundaries at
or near room temperature. As a result, further investigation into
this material system is necessary for understanding the origin of
its enhanced piezoelectricity.234 To further clarify this
assumption, we characterized the dielectric constant of
0.992(0.95K 0.5 Na 0.5 NbO 3 −0.05LiSbO 3 )−0.008BiScO 3 ce-
ramics at different temperatures, as shown in Figure 10. The
Figure 10. εr−T curve of 0.992(0.95K0.5Na0.5NbO3−0.05LiSbO3)−
0.008BiScO3 ceramics.
εr−T curve measured from −150 to 200 °C shows the
involvement of R−T phase boundaries in this material. This
suggests that enhanced d33 values of this material should be due
to the R−T phase boundary and not a T phase.
4.1.7. Ratio of K/Na. In 2007, our group observed a large
d33 of ∼306 pC/N in KNN-based ceramics by modifying K/Na
ratios,156 and related research by other groups has further
clarified this issue.245−247 In fact, the K/Na ratios of KNN
materials were thought to modify PPT near room temper-
ature,156,186,244−247 helping to enhance their piezoelectric
activity. Although the K/Na ratios strongly affect the
piezoelectric activity of KNN-based ceramics, the optimum
K/Na ratio is very sensitive to the actual compositions of the
KNN-based materials,156,186,244−247 as shown in Table 8. In the
references, the d33 values of KNN-based materials could be
improved by changing the K/Na ratio as their TO−T is
intrinsically shifted. 156,186,244−247 Zhai,245 Kang, 246 and
Chang247 et al. also promoted the piezoelectric activity of
KNN-based ceramics by similar methods, but the K/Na ratio is
obviously different. As a result, the piezoelectric properties of
KNN-based ceramics were enhanced mainly due to the
evolutions of phase structure induced by changing the K/Na
ratio.
2570
Review
Table 8. Effect of K/Na Ratio on Piezoelectric Properties of
KNN-Based Ceramics
d33 (pC/ Tc
composition N) kP (°C) ref
(KxNa0.96−xLi0.04)(Nb,Ta,Sb)O3 306 0.48 Wu156
(x = 0.38)
0.95(KxNa1−x)NbO3−0.05LiSbO3 280 0.49 Wu186
(x = 0.40)
(KxNa1−x)0.95Li0.05(Nb,Ta)O3 242 0.46 Wu244
(x = 0.42)
(KxNa1−x)0.94Li0.06NbO3 (x = 0.50) 220 0.43 Zhai245
(NaxKy)(Nb,Sb)−LiTaO3 183 0.33 Kang246
(KxNa0.96−xLi0.04)(Nb,Ta)O3 291 0.54 Chang247
(x = 0.44)
4.1.8. Other Ions. As discussed before, chemical
modifications (ion substitution (Li+, Ta5+, Sb5+), ABO3, etc.)
can improve the piezoelectric activity of KNN materials by
constructing O−T phase boundaries. However, other elements
may also affect the piezoelectricity of KNN materials,118,399−405
as shown in Table 9. We can observe from Table 9 that the
piezoelectric activity of KNN materials results from ion
substitutions of A and/or B.118,399−405 For example, doping
with Ag+ can enhance the d33 value of KNNST ceramics by
shifting TO−T to near room temperature.118,399 It was found
that the addition of Bi3+ and Zr4+ induces improvement in d33
of KNN by shifting a phase transition from pseudocubic to
orthorhombic phase.401 As a result, different ion substitution
can result in different piezoelectric activity of KNN materials
mainly due to the involvement of different phase bounda-
ries,118,399−405 and the enhancement in their piezoelectricity of
most ceramics is due to the O−T phase boundary.118,399,402
Figure 11a displays the d33 and TC values of ceramics with
different chemical modifications. It was found that the
piezoelectric activity is strongly dependent on the types of
the chemical modifications. In terms of the piezoelectric
activity, Li+-, Ta5+-, and Sb5+-modified KNN ceramics possess
larger d33 values with respect to others. As far as the TC value is
concerned, ceramics doped with Li+ or Li+−Ta5+ have higher
TC values than those doped with other additives. To further
understand the effects of doping elements on the piezo-
electricity, we give some samples and plot the d33 vs TO−T of
KNN ceramics with different ion substitu-
tions,101,102,156,169,182,184,188,193,195,204,214 as shown in Figure
11b. For the same doping elements, the d33 value is very
sensitive to the corresponding TO−T, and the d33 value can be
greatly increased for a TO−T near room temperature. More
interestingly, we found that a higher d33 value can only be
attained with Li+, Ta5+, and Sb5+ codoped KNN ceramics, even
if a similar TO−T is involved.182,193,204 As a result, the
piezoelectric activity of KNN-based materials is strongly
affected by not only the phase boundary but also the TO−T
value. In addition, some other factors also play a part in a
material’s piezoelectric properties, such as poling conditions,169
microstructure,204 and electronegativity.204
4.2. Rhombohedral−Orthorhombic Phase Boundaries
It is well known that a pure KNN undergoes a series of
structural phase transitions as the measurement temperature
increases (see Figure 13): TR−O(−123 °C) → TO−T(210 °C)
→ TC(410 °C).5,248,249 In section 4.1, much attention has been
paid to discussion of the O−T phase boundary of KNN
materials, which has been an effective tool for enhancing their
piezoelectric activity over the past 10 years (refs 101, 102, 132,
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Table 9. Piezoelectricity of KNN-Based Ceramics with Different Ion Substitutions

composition d33 (pC/N) kP Tc (°C) ref
(K0.42Na0.52Li0.04Ag0.02)(Nb0.91Ta0.05Sb0.04)O3 263 0.45 353 Wu118
0.98[(K0.4725Na0.4725Li0.055)0.98Ag0.02(Nb0.98Ta0.02)O3 237 0.39 470 Xiao399
(K0.5Na0.5)0.82Ag0.18NbO3 186 0.43 355 Lei400
(K0.50Na0.50)0.97Bi0.01(Nb0.98Zr0.02)O3 161 0.41 370 Wu401
(K0.5Na0.5)0.94Li0.06(W2/3Bi1/3)0.008Nb0.992O3 282 0.45 Du402
(K0.5Na0.5)0.92Li0.04Sr0.02Nb0.98Sb0.02O3 142 0.38 353 Hao403
(K0.5Na0.5)(Nb0.998Cu0.005)O3 112 0.38 440 Tan404
(K0.48Na0.48Ca0.02)(Nb0.85Ta0.15O3) 155 Coondoo405

Figure 11. (a) d33 vs TC of ceramics with different chemical modifications,12,97,101,102,104,106−118,166,277−285,392−405 and d33 vs TO−T values of the
ceramics.101,102,156,169,182,188,184,193,195,204,214

Figure 12. Phase diagrams of (a) (K0.5Na0.5)(Nb1−xTax)O3254 and (b) (1−y)K0.5Na0.5NbO3 −yBaZrO3397 ceramics.

Figure 13. Phase transitions of a pure KNN.

151−157, 159−168, 170−178, 182−197, 199−218, 220, 221,
224, and 229−247). However, the R−O phase boundary of
KNN is often neglected, as such a phase transition is at low
temperatures (ca. −123 °C)248,249 and provides a poor d33.392
Recently, additives have been used to increase the TR−O values
of KNN, including Sb5+,251,253,392 Ta5+,254 AZrO3 (A = Ba2+,
Sr2+, Ca2+),397,398 BiScO3,252 etc.250,255,256,258−263 For example,
the TR−O value of (K0.48Na0.52)(Nb,Sb)O3 can be tuned to near
room temperature by refining the Sb content (see Figure 9);
thereby an improved d33 (∼230 pC/N) was demonstrated due
to the coexistence of R−O ferroelectric mixed phases.251 In
2571
addition, it was found that doping with Ta5+ could decrease
both TC and TO−T and increase TR−O of KNN,254 similar to
Sb5+.251,392 However, the TR−O value of Ta-doped KNN
ceramic could not reach room temperature in the investigated
composition ranges (see Figure 12a),254 showing that the R−O
phase boundary is difficult to induce by chemical modification.
Figure 12b plots the phase diagram of (1−x)K0.50Na0.50NbO3−
xBaZrO3 solid solutions. For a pure KNN ceramic, the addition
of AZrO3 (A = Ba2+, Sr2+, or Ca2+) can shift its TR−O to room
temperature.397,398 Although the R−O phase boundary can be
formed in KNN,250−252 the d33 value of ≤230 pC/N is usually
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poorer with respect to those with O−T phase boundaries, as KNN, as collected from these references.250−254,397,398 The
shown in Table 10. Their d33 values are determined not only by addition of ions or ABO3 materials (e.g., Sb5+,251,392 Ta5+,254
BaZrO3,397 CaZrO3,398 SrZrO3,398 etc.) could simultaneously
Table 10. Piezoelectric Properties of KNN-Based Ceramics increase TR−O and decrease TO−T of KNN materials. As a result,
with TR−O it is reasonable that the R−T phase boundary should be formed
in KNN materials by controlling the composition ratios of the
d33
(pC/ TPPT Tc doped additives.
material system N) kp (°C) (°C) ref According to a number of references, we developed new
(Na0.52K0.48)(Nb1−ySby)O3 230 ∼Tr ∼190 Zuo251 methods to form new phase boundaries (e.g., R−T) in KNN
(y = 0.09) materials, as shown in Figure 14. Some additives were able to
(1−x)KNN−xCaZrO3 154 0.32 ∼Tr 320 Liang250
(x = 0.04)
(1−x)(Na0.5K0.5)NbO3− 210 0.45 ∼Tr 340 Zuo252
xBiScO3 (x = 0.02)

their R−O phase boundary but also by their chemical

modification types,250−252 and unfortunately the d33 is usually
increased by sacrificing TC.250−252 Although R−O KNN
materials possess a poor comprehensive performance of d33
and TC, it may help to design new phase boundaries (e.g., R−
T) by simultaneously moving TO−T and TR−O close to room
temperature.106−110 Detailed analysis is provided in section 4.3.
4.3. Rhombohedral−Tetragonal Phase Boundaries
As shown in sections 4.1 and 4.2, researchers have invested
much energy into the construction of two kinds of phase Figure 14. Diagram for constructing new phase boundaries in KNN
boundaries (i.e., O−T (refs 101, 102, 132, 151−157, 159−168, ceramics.
170−178, 182−197, 199−218, 220, 221, 224, and 229−247)
and R−O250−254,397,398) in KNN materials because of their
decrease TO−T of KNN to room temperature, including LiAO3
enhanced piezoelectric behavior, and a number of construction
(A = Nb 5+ , 101,172 Ta 5+ , 102,193,196 Sb 5+ 182,183,186,187 ),
methods were systematically addressed. More recently, several
Bi0.5B0.5TiO3 (B = Na+,215,216 K+,217 Li+ 218), CTiO3 (C =
attempts were made to shift the R−O boundary to near room
Ba2+,219 Sr2+,219 Ca2+ 223), etc.; their TR−O could be shifted to
temperature,250−254,397,398 and a low piezoelectric activity of d33
room temperature by the addition of DZrO3397,398 (D = Ba2+,
≤ 230 pC/N could be induced. In addition, it was proved that
Sr2+, Ca2+), BiEO3 (E = Sc3+,226,252 Al3+,225 Fe3+,227 Co3+ 228),
two kinds of phase boundaries (i.e., R−O and O−T) in KNN
Ta5+,254 Sb5+,251,253,257,392 etc. We were ultimately able to
belong to a polymorphic phase boundary (PPB), rather than a
induce the R−T phase boundary in KNN by doping different
typical morphotropic phase boundary (MPB).17,18,182,200,205
additives, and a series of KNN-based material systems with R−
The materials with PPBs possess a strong temperature
T phase boundaries has been developed.106−117,256,277,284,285 In
dependence of piezoelectric properties.17,18,182,200,205 At the
2013, our group first reported a high d33 value of ∼425 pC/N
same time, the d33 value of R−O or O−T KNN-based ceramics
in 0.96(K0.5Na0.5)0.95Li0.05Nb1−xSbxO3-0.04BaZrO3 ceramics by
is still poorer with respect to the lead-based ones. Faced with
constructing the R−T phase boundary (see Figure 15),256
such a bottleneck, we asked ourselves how to clarify these issues
matching previously reported results (∼416 pC/N) of textured
concerning KNN. Previously, it was reported that the R−T
KNN-based ceramics.12 In this paper, both Sb5+ and BaZrO3
phase boundary of PZT possesses a weak temperature
dependence of piezoelectric properties and a large d33;4,5
thus, we wanted to know whether a similar R−T phase
boundary could be induced for further improving both the
piezoelectric properties and the temperature stability of KNN
materials. By reviewing a number of the references, it seems
feasible to design a R−T phase boundary in KNN according to
the regulation of the formation of R−O and O−T phase
boundaries by doping in additives (refs 101, 102, 132,
151−157, 159−168, 170−178, 182−197, 199−218, 220, 221,
224, 229−247, and 250−254). Table 11 displays the influences
of different additives on the phase transition temperatures of

Table 11. Effect of Additives on the Phase Transition

Temperatures of KNN Ceramics

substitution (1 mol %) Ta5+ Sb5+ CaZrO3 BaZrO3 SrZrO3

TC (°C) −6.5 −25.1 −28.0 −28.0 −32.0
Figure 15. Phase diagram of KNLNSx−BZ ceramics. (Inset)
TO−T (°C) −4.0 −10.7 −11.0 −7.0 −13.0 Temperature dependence of εr and the composition dependence of
TR−O (°C) +2.3 +14.8 +17.0 +19.0 +19.0 d33.256

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Table 12. Piezoelectric Properties of KNN-Based Ceramics with TR−T

material system d33 (pC/N) kp Tc (°C) ref
(Na0.52K0.40)(Nb0.84Sb0.08)O3−(0.08−x)LiTaO3−xBaZrO3 (x = 0.025) 365 0.45 ∼170 257
KNN−BaZrO3−LiSbO3 344 0.324 ∼176 258
(1−x)K0.5Na0.5Nb1−xSbxO3−xBi0.5Na0.5TiO3 380 0.35 ∼267 255
0.96(K0.5Na0.5)0.95Li0.05Nb1−xSbxO3−0.04BaZrO3 425 0.50 ∼197 256
(1−x)(K0.48Na0.52)(Nb0.95Sb0.05)O3−xBi0.5(Na0.7K0.2Li0.1)0.5ZrO3 380 0.46 290 260
(0.97−x)K0.48Na0.52NbO3−0.03Bi0.5(Na0.7K0.2Li0.1)0.5ZrO3−xB0.5Na0.5TiO3 285 0.40 347 261
0.992(K0.46Na0.54)0.965Li0.035Nb1−xSbxO3−0.008BiScO3 325 0.48 358 109

Figure 16. Relationship between phase boundary and d33 of (1−x)(K1−yNay)(Nb1−zSbz)O3−xBi0.5(Na1−wKw)0.5ZrO3 ceramics: (a) y = 0.48, z = 0.05,
w = 0.18; (b) x = 0.04, z = 0.05, w = 0.18; (c) x = 0.04, y = 0.48, w = 0.18; (d) x = 0.04, y = 0.48, z = 0.05.106

were used to simultaneously decrease the TO−T values and
increase the TR−O values of KNN materials.251,397 However, we
can observe from Table 12 that the ceramics often possess low
TC values of <200 °C even if a large d33 (344−425 pC/N) was
observed.256−258 As a result, it is necessary to attain both a
higher TC and a larger d33 in KNN when designing new phase
boundaries.106−117
In the past, it was reported that doping with CZrO3 (C =
Ba2+, Sr2+, Ca2+) can form three kinds of phase transition
temperatures (i.e., TC, TR−O, and TO−T) in KNN.397,398 In
addition, the effects of CZrO3 on their TC, TR−O, and TO−T are
almost independent of the types of A site (e.g., Ba2+, Sr2+,
Ca2+), and therefore, Zr4+ plays an important role in the phase
transition temperatures (especially TR−O).397,398 Previously, it
was reported that adding Bi3+ can shift the TO−T of KNN
materials.119,401 As a result, Bi3+ and Zr4+ could be used to tune
the TR−O and TO−T of KNN, forming the R−T phase boundary
by simultaneously shifting TR−O and TO−T using additives
containing two such elements. To maintain valence balance, we
constructed the new material Bi0.5M0.5ZrO3 (M = Na, Li, K, Ag,
(Na, Li), (Na, K), (Na, Ag), (K, Li), (Ag, Li), (Ag, Li), (Ag, K),
(Na, K, Li), (Na, K, Ag), (Na, Li, K), etc.),277 which was used
to modify the KNN-based materials (see Figure 14). As a result,
we developed new KNN-based material systems consisting of
(1−x)(K,Na)(Nb,B)O3−xBi0.5M0.5ZrO3,106−117,277 where B =
none, Sb5+, and Ta5+; M = Na, Li, K, Ag, (Na, Li), (Na, K),
(Na, Ag), (K, Li), (Ag, Li), (Ag, Li), (Ag, K), (Na, K, Li), (Na,
K, Ag), (Na, Li, K), etc.277 The piezoelectric properties of KNN
2573
can be modified by forming different phase boundaries using
the optimization of the B and M elements in the
materials.106−117,260,261,277,284,285 In addition, it is of great
importance to note that the R−T phase boundary can be
induced by using the additives mentioned above, leading to a
large d33 of 400−490 pC/N.106−117,277,284,285 For example, a
complicated system consisting of (1−x)(K1−yNay)(Nb1−zSbz)-
O3−xBi0.5(Na1−wKw)0.5ZrO3 (0 ≤ x ≤ 0.05, 0.40 ≤ y ≤ 0.68, 0
≤ z ≤ 0.08, and 0 ≤ w ≤ 1) ceramics was developed and
prepared via the conventional solid-state method,106 and the
R−T phase boundary was constructed by refining the x, y, z,
and w values of such a material system,106 i.e., 0.035 < x <
0.045, 0.44 ≤ y ≤ 0.64, 0.02 < z ≤ 0.05, and 0 ≤ w ≤ 1 (see
Figure 16). By forming the R−T phase boundary, a good
comprehensive performance of d33 and TC (e.g., d33 ≈ 390−490
pC/N and TC ≈ 217−304 °C) was also shown.106 More
importantly, we further studied the role of M in (Bi0.5M0.5ZrO3)
in the piezoelectric properties of 0.96(K 0.48 Na 0.52 )-
(Nb0.95Sb0.05)O3−0.04(Bi0.5M0.5)ZrO3 ceramics.277 The d33
was found to be strongly dependent on the nature of M
because of the change of the R−T phase transition temperature
(TR−T), and the ceramics have high d33 values of 450−490 pC/
N, apart from those doped with Li+.277 As a result, we were able
to realize a larger breakthrough in the piezoelectric activity of
KNN by forming R−T phase boundaries, and the TR−T leads to
different d33 values. In addition, a series of KNN binary or
ternary systems with R−T phase boundaries was prepared
according to our objective of realizing both high TC and d33
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values. 106−117,260,261,396 For example, lead-free (1−x)-
(K0.48Na0.52)(Nb0.95Sb0.05)O3−xBi0.5(Na0.7K0.2Li0.1)0.5ZrO3 ce-
ramics show a high d33 of ∼380 pC/N as well as a high TC
of ∼290 °C (see Figure 17);260 a high d33 of ∼285 pC/N and a
Figure 17. Phase diagram of (1−x)KNNS−xBNKLZ ceramics. (Inset)
Thermal stability of the d33 value.260
high TC of ∼347 °C was also found in the ternary system
consisting of (0.97−x)K0.48Na0.52NbO3−
0.03Bi0.5(Na0.7K0.2Li0.1)0.5ZrO3−xB0.5Na0.5TiO3 with an R−T
phase boundary.261 In addition, good comprehensive perform-
ance of d33 and TC was also observed in other KNN material
systems (see Figures 16−18).106,109,260 As a result, the
Figure 18. Phase diagram of the KNLNSx−BS ceramics. (Inset)
Composition dependence of the d33 values.109
piezoelectric activity of KNN could be dramatically enhanced
by forming R−T phase boundaries using the refinement of
material systems,106−112,256,260,261,277,284,285,396 and both a large
d33 and a high TC could be realized by optimizing their
compositions.106−117,277,284,285,396
As far as KNN-based materials are concerned, we compared
our results with previously reported ones (see Figure 19). One
can see from Figure 19a that the R−T phase boundary is a
more useful way to promote the piezoelectric activity of KNN-
based ceramics with respect to others (e.g., O−T and R−O). In
addition, the comprehensive performance of d33 and TC in
KNN is superior to those of BT- and BNT-based materials (see
Figure 19b). As a result, the R−T phase boundary can greatly
promote the piezoelectric activity of KNN-based ce-
ramics,106−117,260,261,277,284,285,396 and our finding may pave
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the way for practical applications to be “Lead-free at last”. We
believe that such material systems with R−T phase boundaries
are very promising candidates for potassium−sodium niobate
piezoceramics.
4.4. Dopant Engineering
It is well known that the piezoelectric properties of KNN can
be greatly promoted by constructing phase boundaries using
different additives, that is, the formation of phase boundaries
driven by additives plays a large part in their improved
piezoelectric properties. However, other factors may affect the
electrical properties of KNN-based materials. In this section, we
will briefly review the dopant engineering in KNN-based
materials.
4.4.1. Doping with Equipollent Metals. Equipollent
metals are usually used to substitute the A or B site of KNN,
where Li+ often substitutes the A site101,166−173 and Sb5+ (refs
182−192, 251, and 392) and/or Ta5+ (refs 102, 162, 163,
193−203, and 254) are often used to replace the B
site.12,156,157,204−214 The main objective of these additives is
to induce the formation of phase boundaries by shifting phase
transition temperatures (T R − O , T O− T , and T C ) of
KNN.101,102,156,157,162,163,166−203,251,254 For example, the Li+
can decrease the TO−T as well as increase both TR−O and TC
of KNN,101,166−173 and doping with Sb5+ or Ta5+ can decrease
both TO−T and TC as well as increase TR−O of KNN (see Figure
9 and 12a).251,254 The Li, Ta, or Sb can cause the shift of three
kinds of phase transition temperatures (TR−O, TO−T, and TC) of
KNN materials (refs 101, 102, 156, 157, 162, 163, 166−203,
251, and 254), and thus, the enhanced piezoelectric properties
of Li+-, Ta5+-, or Sb5+-modified KNN materials originate from
the formation of different phase boundaries. As a result,
different phase boundaries can be effected by introducing one
or more elements to KNN, the main advantage of these
elements being to simultaneously shift its TR−O, TO−T, and TC.
Other factors may also be responsible for the enhanced
piezoelectric activity of KNN. For example, Li, Ta, and Sb have
the same valence as the A or B sites of KNN, which can avoid
the generation of certain defects. Recently, Safari et al.267
proposed that sp3 hybridization of the covalent over the ionic
bond should result in enhanced d33 values of (Li, Ta, Sb)
codoped KNN ceramics because the higher electronegativities
of Ta5+ and Sb5+ can increase the covalence of the bonds with
respect to Nb5+. Zhang et al.204 also proposed that the high
electronegativity of Sb5+ is responsible for the enhanced
piezoelectric properties of KNN-based ceramics. As a result,
some factors (electron configuration, ligand field theory,
covalence, etc.) are also considered for improving the electrical
properties by doping additives.
4.4.2. Doping with Aliovalent Metals. 4.4.2.1. Aliovalent
Metals at the Nb Site. Aliovalent metals are often used to tailor
the electrical properties of KNN materials by forming point
defects.128,145,267,279−281,406−415 It is usually accepted that the
defect dipoles formed by acceptor dopants for charge balance
will prohibit domain−wall motion and then result in “harden-
ing” of KNN. In the past, Cu-modified KNN systems have been
extensively studied because of their high mechanical quality
factor;267 such a high Qm is due to the “hardening” effect. For
example, Hoffmann et al. proposed that the “hardening”
behavior of Cu-doped KNN ceramics originates from the
impediment of domain−wall motion induced by two kinds of
defect complexes with oxygen vacancies ((CuNb ‴ − V••O )′ and
•• •• • 267,411,414
(VO − CuNb ‴ − VO ) ). For Mn-modified KNN single
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Figure 19. Room-temperature d33 as a function of TC for (a) KNN-based ceramics and our work90−265,277,284,285,392−405 and (b) BNT, BT-based
ceramics, and our work.16,17,35−90
crystals, the conductivity can be more quickly decreased after
annealing under the same conditions because the Mn2+ valence
gradually becomes higher by absorbing electron holes.128
Similarly, it was also found that Mn2+ can absorb the free
carrier holes from the volatilization of alkaline ions in Mn2+-
doped KNN thin films, inducing enhanced ferroelectric
properties.408,409,412 Yao et al. reported that titanium diffusions
strongly affected the composition, structure, and dielectric
properties of Ti4+-doped KNN thin films because both holes
and oxygen vacancies will be generated, as shown in eqs 2 and
3.407
Nb
Ti ↔ Ti′Nb + h• (2)
Nb2O5
2TiO2 ←⎯⎯⎯→ 2Ti′Nb + 4OO + V ••
O + 2e′ (3)
Recently, the influences of elements with a higher valence on
the properties of KNN materials have been studied, and it was
found that the concentration of oxygen vacancies is restrained
because W6+ can replace the Nb site of KNN (see eq 4).415 The
dielectric properties can be modified well by controlling the
type of defect and the concentration of oxygen vacancies.
2WO3 + V •• ••
O = 2W Nb + 6O (4)
As a result, the electrical properties of KNN can be modified by
tailoring the different defect types induced using aliovalent
metals.
4.4.2.2. Aliovalent Metals at the (Na, K) Site. In the past,
substitution of some aliovalent ions (Ba2+,137,148 Pb2+,416
Dy3+ 417) at the A site can promote the piezoelectric properties
of KNN materials because of different defect structure and
improved microstructure.416−419 Importantly, we illuminated
the effects of different defect types on the electrical properties
of KNN-based materials by introducing aliovalent elements to
the A site. For example, an extra electron (e−) can be easily
generated for keeping valence balance when Ba2+ is used to
replace the A site of KNN-based materials (see eq 5).148
Ba′K → BaK + e− (5)
At the same time, the K+ vacancy is formed due to the
evaporation of K+ during processing and preparation,419 as
shown in eq 6.
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Review
VK → V′K + h+ (6)
As a result, the vacancy and electron will be easily recombined
and eliminated during processing, which results in increasing
resistivity. In addition, the “softening” characteristics also
promote their piezoelectric properties.148 It was reported that
Dy3+ substitutions at the A site in KNN can be expressed by eq
7.417
K 0.5Na 0.5NbO3
Dy2O3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ 2Dy ••
Na
+ 4V′Na + 3OO (7)
For maintaining charge neutrality, electrons will be generated
due to Dy3+ as a donor and a Na vacancy was also observed.
The net dipole moment of two defects may be formed,
inducing the maximum dielectric constant of Dy2O3-doped
KNN ceramics.417
High piezoelectricity of KNN-based materials mainly
originates from the formation of phase boundaries driven by
different additives, but other factors should not be neglected,
such as ion types (e.g., electron configuration, ligand field
theory, covalence, etc.), defect types, and their relation with
electrical properties, and so on. Understanding dopant
engineering will benefit the development of physical mecha-
nisms for enhanced electrical properties.
4.5. Supplementary Tools
As mentioned above, many attempts have been made to
promote the piezoelectric activity of KNN-based materials by
inducing three kinds of phase boundaries [e.g., O−T (refs 101,
102, 132, 151−157, 159−168, 170−178, 182−197, 199−218,
220, 221, 224, and 229−247), R−O,251,254,392,397,398 and R−
T106−117,256,260,261,277,284,285,396], including ion substitutions
(Li+, Ta5+, Sb5+, etc.), the formation of solid solutions, K/Na
ratio, and others. In addition, other methods besides the
construction of phase boundaries also affect the piezoelectricity
of KNN-based materials, such as sintering temper-
atures,165,420−432 reactive template grain growth,12,203,433−446
spark-plasma sintering, 1 2 7 , 4 4 7 − 4 5 2 non sto ichiom e-
try,113,166,168,453−467 two-step sintering,245,480−483 single crys-
tal,120,484−508,547−551 poling conditions,166,169,265,520−522 sinter-
ing aids and sintering atmosphere,130,140,143,147,498,523−546 thin
films,553−590 and extrinsic factors (density,3,121,127,135,249 grain
size,124,132,271,537,539,610−613 domain struc-
ture,446,268,269,406,614−622 etc.). In this section, we briefly
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Table 13. Effect of Sintering Temperatures on the Piezoelectric Activity of KNN-Based Ceramics
compositions Tsintering (°C) d33 (pC/N) kP Tc (°C) ref
0.96K0.46Na0.54Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3 1075 465 0.43 233 Wu112
[(Na0.535K0.480)0.966Li0.058](Nb0.90Ta0.10)O3 1090 268 0.46 445 Zhao165
0.058LiNbO3−0.942(Na0.535K0.480)NbO3 1060 314 0.41 490 Zhao177
(Na0.535K0.485)0.926Li0.074(Nb0.942Ta0.058)O3 1000 276 0.46 ∼450 Li421
0.92(Na0.535K0.48)NbO3−0.08LiNbO3 950 280 0.483 Li and Wang422

Table 14. Piezoelectric Properties of KNN-Based Ceramics Prepared by the RTGG Method
composition orientation d33 (pC/N) kP Tc (°C) ref
(K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3 ⟨001⟩ 416 0.61 253 Satio12
(Na0.50K0.47Li0.03)(Nb0.8Ta0.2)O3 + MnO2 + Li2CO3 ⟨h00⟩ 310 0.46 ∼320 Cho203
(K0.5Na0.5)(Nb0.97Sb0.03)O3 ⟨001⟩ 208 0.64 352 Chang433
(K0.463Na0.537)0.946Li0.054NbO3 ⟨001⟩ 254 0.43 450 Hao434

Table 15. Piezoelectric Properties of KNN-Based Ceramics Prepared by Other Nonconventional Techniques
composition preparation technique Tsintering (°C) d33 (pC/N) kP Tc (°C) ref.
(Na0.52K0.44Li0.04)(Nb0.86Ta0.06Sb0.08)O3 SPS + sol−gel 296 0.50 Wang448
(Li0.04K0.44Na0.52)(Nb0.85Ta0.15)O3 SPS 900 225 0.44 Li450
(Na0.535K0.485)0.95Li0.05(Nb0.8Ta0.2)O3 SPS 900 243 0.46 450 Li451

introduce the influences of these methods on the electrical
properties and the corresponding physical mechanism.
4.5.1. Sintering Temperature. The sintering temperature
is usually thought to strongly affect the piezoelectric activity of
KNN-based materials because of the involvement of oxygen
vacancies induced by the loss of K+ and Na+ during the
sintering process.112,165,177,421−431,470 However, it is difficult to
maintain the stoichiometric compositions of KNN materials
due to this facile loss of K+ and Na+.
Recently, sintering with compensation of the alkali metal loss
has been conducted to solve this issue, whereby enhanced d33
values of 268−314 pC/N could be obtained,112,165,419−431 as
shown in Table 13. For example, Zhang et al.165 prepared
LiTaO3-doped (K,Na)NbO3 ceramics using both optimum
sintering temperatures and excess Na+ with the aim of
controlling Na+ loss, and a high d33 value of ∼268 pC/N was
induced, which is much larger than those doped with LiTaO3
prepared by the conventional methods.102,198 In addition, they
investigated the electrical properties of 0.942(Na0.535K0.480)-
NbO3−0.058LiNbO3 by emphasizing the influence of sintering
temperatures as well as excess Na+,177 and an enhanced
piezoelectric coefficient of ∼314 pC/N was also attained when
the material was sintered at 1060 °C. Li et al.421,422 also
investigated the influences of the sintering temperature on the
phase structure, microstructure, and electrical properties of
(Na 0.5 35 K 0 .48 5 ) 0.9 26 Li 0 .07 4 (Nb 0.9 42 Ta 0. 058 )O 3 and 0.92-
(Na0.535K0.48)NbO3−0.08LiNbO3 ceramics, showing that the
optimized sintering temperature is a critical factor to determine
their d33. More recently, we realized a large d33 (∼465 pC/N)
in 0.96K0.46Na0.54Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3
ceramics by optimizing the sintering temperatures, where the
TR−T values and alkali metal content could be tailored by
changing their sintering temperatures.112 As discussed above,
the main objective of this research is to suppress K+ and Na+
loss by optimizing the sintering temperatures as well as
compensating for the volatile elements according to the
nominal nonstoichiometric formulas,112,165,177,421−431 in which
the sum of molar fractions of atoms substituting the A site in
ABO3 is above 1 mol, so that the superfluous parts can
2576
compensate for their losses during processing at a temper-
ature.112,165,177,421−431
4.5.2. Reactive Template Grain Growth Method.
Excellent piezoelectric parameters (dijk, gikk, kij, etc.) are
required for some piezoelectric devices.468,469 The reactive
template grain growth (RTGG) method could effectively
improve the piezoelectric coefficients of a material due to more
efficient alignment of the polar vectors, resulting in the increase
of poling efficiency.12,203,433,434,468,469 For KNN material
systems, the initial breakthrough was the realization of a large
d33 value (∼416 pC/N) in (K0.44Na0.52Li0.04)-
(Nb0.86Ta0.10Sb0.04)O3 ceramics prepared by the RTGG
method.12 In this work, the d33 value was found to match
those of most PZT ceramics, spurring further interest in
improving the piezoelectricity of KNN-based ceramics by the
RTGG method.12,203,433,434,468,469 For example, ⟨001⟩-oriented
(K0.5Na0.5)(Nb0.97Sb0.03)O3 ceramics were prepared by the
RTGG methods using NaNbO3 templates;433 these materials
possessed enhanced piezoelectric properties of kp = 0.64, k31 =
0.37, d33 = 208−218 pC/N, and d31 = −82 pC/N. Although
textured KNN-based ceramics have better piezoelectric proper-
ties with respect to nontextured ones owing to the easier
rotation of the polarization axis during the poling process (see
Table 14),12,203,433,434,468,469 they are not suitable for practical
applications due to high costs and their complicated
preparation process.
4.5.3. Spark-Plasma Sintering. Special sintering techni-
ques including hot pressing and spark-plasma sintering (SPS)
have been used in order to overcome the difficulties
encountered in fabricating high-density KNN materials. SPS
has a number of advantages, such as a rapid heating rate and
short soaking time.127,447−452 Related research has shown that
the SPS method can effectively promote the piezoelectric
activity of KNN by inducing improved microstruc-
ture,127,447−452 as shown in Table 15. Li et al.127,447,450,451
extensively studied the microstructure and electrical properties
of KNN-based ceramics prepared by SPS methods. For
example, in 2006, the SPS was explored to solve the poor
densification of a pure KNN ceramic,127 and a d33 value of 148
pC/N was obtained in highly dense KNN ceramics (theoretical
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Table 16. Piezoelectric Properties of Nonstoichiometric KNN-Based Ceramics

compositions d33 (pC/N) kP Tsintering (°C) ref
0.96(K0.46Na0.54+x)Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3 496 0.47 1075 Wu113
(1−x)(Na0.535K0.48)NbO3−xLiNbO3 (x = 0.08) 324a 950 Li and Wang166
(1−x)(Na0.535K0.48)NbO3−xLiNbO3 (x = 0.08) 280 0.483 950 Li and Wang168
(K0.48Na0.48Li0.04)1+x(Nb0.90Sb0.06Ta0.04)O3 (x = 0.01) 310 0.6 1090 Lin461
[(Na0.535K0.48)0.942Li0.058](Nb1−xSbx)O3 (x = 0.06) 298 0.345 1040 Zhang462
[(Na0.535K0.480)0.942Li0.058](Nb0.86Ta0.10Sb0.04)O3 264 0.356 1090 Zhang463
a
Repoling treatment.

density > 99%) at a low processing temperature of ∼920 °C. In
addition, they also prepared a high-density KNN piezoceramic
by the combination of a facile hydrothermal route and SPS,447
the d33 of which was shown to reach ∼135 pC/N, which is
almost twice as much as those of samples using powders
prepared from the solid-state reaction. More recently, Wang et
al. 448 reported that highly dense (Na 0.52 K 0.44 Li 0.04 )-
(Nb0.86Ta0.06Sb0.08)O3 nanoceramics can be fabricated by SPS
methods using nanopowders (11−34 nm), and a piezo-
electricity of d33 ≈ 296 pC/N was observed, showing that the
combination of nanopowders and SPS techniques are an
effective way to prepare fine-grained potassium−sodium
niobate ceramics with excellent elelctrical properties. These
results show that an enhanced piezoelectric activity of the SPS-
sintered samples could be attributed to the lower sintering
temperatures and the higher densities, which is superior to
those sintered by the conventional pressureless technique.449 In
addition, related investigations were able to more clearly clarify
the relationships between microstructure and electrical proper-
ties of KNN-based materials.127,447−452 As far as practical
applications are concerned, SPS is not as widely applied in
industry as the RTGG method is.
4.5.4. Nonstoichiometry. The composition fluctuations
seriously affect the electrical properties of KNN-based materials
due to alkali metal evaporation, which is a serious issue despite
the significant breakthroughs in its synthesis and character-
ization.453 The deviation from stoichiometry during the
synthesis is a result of the strongly hygroscopic nature of
alkaline carbonates, especially potassium carbonate.454 As a
result, controlling the alkali metal loss in KNN during its
processing and sintering is a critical issue.453,455
It is well known that dense KNN ceramics must endure a
high processing temperature of ∼1100 °C, whereby chemical
composition fluctuations cannot be avoided due to the
evaporation of some elements.113,453−456 In addition, chemical
composition deviation may be also caused during weighing due
to the deliquescence of Na2CO3/K2CO3. As a result, the loss of
alkali metals negatively affects the electrical properties of KNN
materials, and much attention has been focused on how to
maintain the stoichiometric ratios of KNN.166,168,456−467 Table
16 shows the d33 values of published nonstoichiometric KNN-
based ceramics.113,166,168,461−463 Excess alkali metals were used
to suppress the chemical composition fluctuations of KNN-
based ceramics,113,166,168,461−467 and enhanced piezoelectric
properties were observed (see Table 16). These results show
that the calcining and sintering temperatures of KNN have
been strongly affected by the nonstoichiometric con-
tent.282,283,456 The sintering temperatures of KNN were
decreased when the A site was excessive168 and then raised
when the B site was excessive.457 For example, Rubio-Marcos et
al.283 reported that excess K+ may induce a displacement of Li+
from (K0.44+xNa0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3, seriously affect-
2577
ing their piezoelectric activity by changing the stabilization of
the crystalline symmetries. More importantly, nonstoichiomet-
ric KNN-based ceramics possess much larger d33 values than
stoichiometric ones with the same composition, as shown in
Tables 16 and 17.101,184,212 In 2014, we attained a high
Table 17. Piezoelectric Properties of Stoichiometric KNN-
Based Ceramics
d33
compositions (pC/N) kP ref
(1−x)(Na0.50K0.50)NbO3−xLiNbO3 (x = 0.08) 164 0.35 Guo101
0.94(K0.5Na0.5)NbO3−0.06LiSbO3 212 0.46 Lin184
Li0.02(Na0.55K0.45)0.98(Nb0.77Ta0.18Sb0.05)O3 256 0.42 Yoo212
0.96(K0.46Na0.54+x)Nb0.95Sb0.05O3 436 0.44 Wu113
−0.04Bi0.5(Na0.82K0.18)0.5ZrO3
piezoelectric activity (e.g., d33 ≈ 496 pC/N and kp ≈ 47%) in
0.96(K0.46Na0.54+x)Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3
ceramics by doping nonstoichiometric sodium,113 and a
rhombohedral−tetragonal phase boundary was constructed in
ceramics with a wide Na+ nonstoichiometry.113 A higher d33
value was observed in ceramics with an excess of 0.5% Na+ with
respect to those with stoichiometric ratios.113 Thus, the
addition of nonstoichiometric alkali metals makes a large
contribution to promoting the piezoelectric activity of KNN-
based ceramics.
Previously, it was shown that nonstoichiometric KNN-based
ceramics with A/B < 1 possess an improved piezoelectricity due
to the microstructure evolutions induced by the formation of a
ferroelectric secondary phase.132,135,457,465 For example, Rubio-
Marcos et al.132 systematically studied the effects of A/B (A =
(K0.44Na0.52Li0.04), B = (Nb0.86Ta0.10Sb0.04), A/B = 0.94) on the
phase structure and electrical properties of (K0.44Na0.52Li0.04)-
(Nb0.86Ta0.10Sb0.04)O3 ceramics, and the electrical properties of
nonstoichiometric compositions were found to improve due to
good homogeneity induced by the grain growth as well as the
presence of a secondary ferroelectric tungsten−bronze phase
(e.g., K3LiNb6O17). As a result, the effects of nonstoichiome-
tricity and stoichiometricity on the microstructure and electrical
properties of KNN-based materials require further clarification,
and further physical analysis should be conducted.
4.5.5. Two-Step Sintering. The normal sintering
technique is to heat the green compact at a given rate; then
the sample is kept at a higher temperature in order to reach the
maximum density. However, it is difficult to achieve a material
with high density, homogeneous microstructure, and small
grain size by normal sintering. In 2000, a two-stage sintering
(TSS) technique developed by Chen et al. was shown to
resolve this issue.546 In the TSS method, the full densification
without grain growth after the second-step temperature can be
achieved by the competition between the driving forces of grain
boundary-controlled densification and grain boundary-con-
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trolled grain growth.114,245,471−483,546 First, the green samples
are heated to a certain temperature for guaranteeing a uniform
pore microstructure (relative densities > 75%) and minimizing
grain growth; they are then cooled and held at a lower
temperature for a long dwell time, where a low sintering
temperature results in decreased grain growths, and a long
dwell time provides enough energy for improving its density.546
Slower kinetics are involved when second-step sintering
proceeds in a frozen microstructure, but it is enough to achieve
full density and suppress grain growth.114,245,471−483,546
To suppress or eliminate grain growth of electroceramics
during sintering, the TSS technique has attracted much
attention because it is possible to decrease the grain size and
improve the density of sintered samples. For solving the narrow
processing window of a ceramic, the TSS technique has also
been used to widern the sintering temperatures of lead-based
and lead-free piezoceramics, 114,245,471−483,546 such as
BaTiO3,471−475 Bi0.5Na0.5TiO3,476−478 BiScO3−PbTiO3,479 and
K0.5Na0.5NbO3.114,245,480−483 The processing procedure for this
method is summarized in Figure 20: The samples are first
Figure 20. Program schedule of conventional sintering and two-step
sintering.
heated to a high temperature (T1) in order to obtain a
relatively high density and then are rapidly cooled and held at a
low temperature (T2). Usually, the piezoelectricity of KNN-
based ceramics is very sensitive to the sintering temper-
atures,112,165,177,421−431,470 that is, enhanced piezoelectric
activity can be only attained in a narrow sintering temperature.
However, the TSS method is suitable for preparing KNN-based
ceramics because the ceramics can be densitified by eradicating
the pores due to the decreased loss of the alkali metals with a
low melting point.114,245,480−483 For example, a pure KNN
ceramic was prepared by the TSS method,482 and the resulting
dense microstructure led to its enhanced piezoelectricity. In
addition, the sintering temperature (T2) range can be widened
significantly for pure or chemically modified KNN ceramics
using TSS,245,480−483 after which their electrical properties were
mostly improved or maintained. The 0.9625Na0.5K0.5NbO3−
0.0375LiTa0.4Sb0.6O3 ceramics possess good electrical proper-
ties together with a wide sintering temperature range (T2 =
1000−1075 °C) when the TSS technique was used,483 and the
TSS method also widens the sintering temperature range
(1090−1130 °C) of (KxNa1−x)0.94Li0.06NbO3 ceramics and
improves its piezoelectric activity.245 Recently, we also realized
a high d33 (348−416 pC/N) and wide sintering temperatures
(800−1130 °C) in 0.955(K0.42Na0.58)(Nb0.96Sb0.04)O3−0.045-
(Bi0.5K0.5)0.90Zn0.10ZrO3 ceramics using the TSS technique.114
As a result, the TSS technique can improve the density and
widen the sintering temperatures of KNN-based material
systems, resulting in an enhanced d33 value.
4.5.6. Single Crystals. The ferroelectric domains of
polycrystalline piezoceramics cannot be aligned completely
along one direction during poling owing to their randomly
oriented grains, easily resulting in degraded electrical proper-
ties. However, the domains of single crystals can be more easily
rotated during the poling fields.120,484−508,549−551 As a result,
single crystals may become an effective way to improve the
piezoelectric activity of alkali niobate materials by controlling
their domain engineering and crystal orientations (refs
484−493, 498, 504−509, and 547−551). Several methods
have been used to prepare KNN-based single crystals, such as
solid-state crystal growth,485,498,505,507,508 the flux meth-
od,486,487,490,491,493 the Bridgman method,181 top-seeded
solution growth,488,489,504 and the floating zone method.492
Table 18 shows the piezoelectric properties of KNN-based
single crystals grown by different methods. Among reported
results, one of the most exciting is that 0.95KNN−0.05LiNbO3

Table 18. Electrical Properties of KNN-Based Single Crystals Grown by Different Methods

compositions preparation method Pr (μC/cm2) εr K33 d33 (pC/N) ref

K0.53Na0.47NbO3 flux method 600 110 Kizaki484
K0.5Na0.5NbO3 solid-state crystal growth 17 1015 80 Uršič485
K0.5Na0.5NbO3 flux method 18 412 148 Gupta486
K0.5Na0.5NbO3 flux method 240 160 Lin487
K0.622Na0.378NbO3 top-seeded solution growth 70 161 Tian488
0.95KNN−0.05LiNbO3 Bridgman 9 185 405 Chen181
(K,Na)(Nb,Ta)O3 top-seeded solution growth 267 0.83 200 Zheng489
K0.53Na0.47Mn0.004Nb0.996Oy flux method 40 Inagaki490
K0.14Na0.86Mn0.005Nb0.995Oy flux method 37 Noguchi491
Mn-doped KNN floating zone method 106 Inagaki492
Na0.5K0.5Nb0.995Mn0.005O3 flux method 52 424 0.64 161 Inagaki490
0.5% Mn−K0.5Na0.5NbO3 flux method 730 270 Lin487
K0.5Na0.5NbO3 with B2O3 flux flux method 32 106 Saravanan493

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crystals grown by the Bridgman method possess an enhanced 1

O2 + 2Nb′Nb + V •• * *
O → OO + 2Nb Nb
piezoelectricity of ∼405 pC/N,181 which is almost two times 2 (8)
that of ceramics with the same composition.101 In addition, Lin
et al. also reported a larger d33 (∼270 pC/N) in 0.5%Mn- 1
modified K0.5Na0.5NbO3 single crystals grown by the high- V ••
O + O2 → O*O + 2h•
2 (9)
temperature solution method using a K2CO3−Na2CO3 eutectic
composition as flux,487 which is also superior to a pure KNN Nb4+ is usually found to exist in KNN single crystals,128
due to the involvement of high domain densities, as shown in leading to a high leakage current density due to the 4d electrons
Table 19. However, as far as piezoelectricity is concerned, most of this ion.552 However, the valence shift of Nb4+ to Nb5+
induced by oxidation treatment can reduce its leakage current
Table 19. Piezoelectricity of Pure and MnO2-Modified KNN density.128 It is well known that oxygen vacancies (V••O ), which
Single Crystal.487 result from the K and Na vacancies during high-temperature
processing, are involved in KNN single crystals.129,181,547,548
compositions TO−T (°C) Tc (°C) d33 (pC/N) Therefore, the leakage current density of KNN single crystals
K0.5Na0.5NbO3 208 423 160 becomes higher when they are annealed under a high-pressure
0.5% Mn−K0.5Na0.5NbO3 193 416 270 oxygen atmosphere.128 According to eq 9, the h• conduction (p
1.5% Mn−K0.5Na0.5NbO3 194 418 230 type) of oxidized KNN single crystals is generated and then
2.0% Mn−K0.5Na0.5NbO3 183 412 220 dominates the leakage behavior at room temperature. As a
result, it is necessary to decrease the formation of h• in KNN
reported results on the piezoelectric properties of KNN-based single crystals in order to further reduce its leakage
single crystals are disappointing because of the involvement of current.128,509 For example, the addition of Mn2+ is an effective
high leakage current induced by defects.128,484,487,490−492,508 way to decrease the leakage current of KNN single
It was thought that the leakage current of KNN single crystals.487,490−492 The increasing Mn valence (Mn2+−Mn4+)
crystals is controlled by the electron−hole (h•) conduction;128 can absorb h• and then realize the objective of lowering its
the formation of h• is demonstrated in eqs 8 and 9.552 leakage current when Mn2+ is used to substitute the Nb site in

Table 20. Preparation Conditions and Electrical Properties of KNN-Based Thin Films553−586

material system substrate preparation method d33 (pm/V) Pr (μC/cm2) ref

K0.5Na0.5NbO3 Pt/Ti/SiO2/Si chemical solution deposition 74.0 553
K0.5Na0.5NbO3 Pt/Ti/SiO2/Si chemical solution deposition 40 554
K0.51Na0.49NbO3 SrRuO3/SrTiO3 hydrothermal method 14 555
K0.5Na0.5NbO3 SrRuO3/SrTiO3 rf magnetron sputtering 12.05 556
K0.5Na0.5NbO3 Pt/TiOx/SiO2/Si chemical solution deposition 7 557
K, NaNbO3 Pt/TiO2/SiO2/Si sol−gel method 3.54 558
K,NaNbO3 LNO/Si rf magnetron sputtering 11.5 559
K0.5Na0.5NbO3 [110] Nb−SrTiO3 sol−gel method 45.1 17.3 560
(K,Na)NbO3 LaNiO3/Si rf magnetron sputtering 58 12 561
K0.5Na0.5NbO3 Pt/TiO2/SiO2/Si sol−gel method 8 562
K0.5Na0.5NbO3 Pt/TiOx/SiO2/Si chemical solution process 46 7 563
K0.5Na0.5NbO3 Pt/TiO2/SiO2/Si rf-magnetron sputtering 64.5 21.1 564
K0.5Na0.5NbO3 (thick film) Pt/Ti/SiO2/Si chemical solution deposition 56 12 565
K0.5Na0.5NbO3 Pt/Ti/SiO2/Si chemical solution deposition 35 9.1 566
Mn2+-K0.5Na0.5NbO3 Pt/Ti/SiO2/Si reactive template method 124* 3.05 567
K0.5Na0.5NbO3 (thick film) Pt/TiO2/Al2O3 screen printing 82.5 568
K0.5Na0.5NbO3 (thick film) platinum foils electrophoretic deposition 40 569
K0.5Na0.5NbO3 (thick film) Pt/Ti/SiO2/Si aerosol deposition method 8.1 570
(K,Na)NbO3−BaCu1/3Nb2/3O3 Pt/sapphire aerosol deposition method 110* 18.03 571
(K0.48Na0.48Li0.04)(Nb0.775Ta0.225)O3 Pt/Ti/SiO2/Si pulsed laser deposition 49 11.3 572
(Na,K)NbO3−LiTaO3 Nb−SrTiO3 hydrothermal method 25 573
0.948K0.5Na0.5NbO3−0.052LiSbO3 Pt/TiO2/Al2O3 aerosol deposition 50 15.5 574
0.94K0.52Na0.58NbO3−0.06LiNbO3 Pt/Ti/SiO2/Si sol−gel method 192 9.7 575
K0.44Na0.52Li0.04Nb0.84Ta0.1Sb0.06O3 SrRuO3/SrTiO3 pulsed laser deposition 53 576
Na0.52K0.44Li0.04Nb0.84Ta0.10Sb0.06O3 Pt/MgO pulsed laser deposition 26.3 577
K0.44Na0.52Li0.04Nb0.84Ta0.10Sb0.06O3 SrRuO3/SrTiO3 pulsed laser deposition 7.5 578
K0.48Na0.48Li0.04Nb0.895 Mn0.005Ta0.10O3 Pt/TiO2/SiO2/Si chemical solution deposition 61 16.1 579
0.92KNN−0.06BaZrO3−0.02Bi0.5Li0.5TiO3 Pt/(001)MgO pulsed laser deposition 24.5 580
K0.4425Na0.52Li0.0375Nb0.8825Sb0.08Ta0.0375O3 Pt/Ti/SiO2/Si sol−gel 9.5 581
K0.44Na0.52Li0.04Nb0.84Ta0.10Sb0.06O3 SrRuO3/SrTiO3 pulsed laser deposition 4 582
K0.44Na0.52Li0.04Nb0.84Ta0.1Sb0.06O3−Mn4+ SrRuO3/SrTiO3 pulsed laser deposition 15 583
K0.44Na0.52Li0.04Nb0.84Ta0.1Sb0.06O3−Mn SrRuO3/SrTiO3 pulsed laser deposition 10 (Ps) 584
K0.5Na0.5Nb0.8Ta0.2O3−Mn Pt/TiOx/SiO2/Si chemical solution deposition 58 7 585
0.95K0.5Na0.5NbO3−0.05CaZrO3−Mn Pt/TiOx/SiO2/Si chemical solution deposition 32 586

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Chemical Reviews
KNN,128,495,497,509 leading to a high remanent polarization (Pr
≈ 40 μC/cm2).
4.5.7. Thin Films. Since the increase in interest in the
piezoelectric activity of KNN-based ceramics, efforts have been
made to prepare corresponding thin films due to their potential
applications for microdevices such as microelectromechanical
systems.552−590 However, two main issues still hinder the
fabrication of high-quality KNN-based films: (i) composition
deviations from stoichiometry and (ii) the loss of alkali oxides
during preparation.553,573,589,590 Table 20 lists the preparation
methods and the corresponding electrical properties of KNN-
based materials in the form of thin films or thick films.553−586
One can observe from Table 20 that the ferroelectric and
piezoelectric properties of KNN-based materials (e.g., thin film
and thick film) can be promoted to varying degrees by some
methods, such as the use of stabilizing agents,553 new
preparation techniques (hydrothermal method),573 excess alkali
metals,557,562 different substrates,552−586 processing condi-
tions,555,567,574 buffer layers,556,559,561,577,582 dopants or ion
substitutions,571−575,577,579−585 orientation,559−561,567,582 an-
nealing atmosphere,564 etc. For a pure KNN thin film,553−564
some factors strongly affect their ferroelectric (Pr = 7.0−21.1
pm/V) and piezoelectric properties (d33* = 40−74 pm/V). For
example, Kim et al. have shown that d33* values of 40 pm/V for
KNN thin films can be attained by doping excess K and Na,554
while the piezoelectric activity can be further promoted up to
d33* = 56−74 pm/V by introducing stabilizing agents
(diethanolamine and ethylenediaminetetraacetic acid)553 or
polyvinylpyrrolidone565 because of the decrease of crystal-
lization temperature and the suppression of the volatility of
alkali ions.587,588 A comparable piezoelectric constant (d33* =
64.5 pm/V) of KNN thin films annealed under a Na2O
atmosphere can be also observed by different preparation
techniques (rf magnetron sputtering).564 It was found that
different substrates also affect the ferroelectric properties of
KNN thin films,568,570 and the Pr values of the films deposited
on Nb-doped SrTiO3560 are much higher with respect to those
deposited on Pt/TiO2/SiO2/Si substrates,558 due to the
involvement of the (110) orientation.560 In addition, the
effects of the orientations on ferroelectric and piezoelectric
properties of a pure KNN thin film were also systematically
studied,559−561,567,582 and [110]-oriented KNN thin films were
found to possess higher Pr values of 17.3 μC/cm2 because the
[110] orientation is its spontaneous polarization direction,
while a large d33 of 50.5 pm/V can be observed in the [001]-
oriented materials560 due to the involvement of reversal of 180°
domains. Also, KNN-based thick films were also prepared, and
their electrical properties were found to be comparable to the
corresponding bulk materials.568,571 For example, it is of great
interest to note that a large d33 of 110 pm/V can be shown in
Ba(Cu1/3Nb2/3)O3-modified KNN thick films owing to the
presence of large grain sizes and abnormal grain growth,571 and
moreover, the KNN thick films also possess a comparable d33 to
the corresponding bulk materials due to their dense micro-
structure.568 Recently, Goh et al. reported a piezoelectric
constant of 25 pm/V in a 480 nm KNN thick film grown at a
very “low” temperature of 130 °C using a new sustainable
hydrothermal method, which results from the decrease of the
loss of alkali metals.573
Although the ferroelectric and piezoelectric properties of
KNN-based films can be improved by these methods,553−564
their electrical properties are still poor when compared to lead-
based or the corresponding bulk materials. Unlike KNN-based
2580
Review
bulk materials, it is difficult to form phase boundaries in the
corresponding material system.575−582 In the past, researchers
have attempted to construct phase boundaries in KNN-based
thin films using the phase boundary compositions of the
corresponding bulk materials,575−582 but the results are
disappointing due to a number of factors (e.g., composition
deviations, lattice mismatch between thin film and substrate,
etc.). As a result, there are considerable challenges for the
development of high-performance KNN-based thin films.
When KNN-based films are prepared, two important factors
(composition deviations and the loss of alkali metals) should be
first considered, and other factors should also be addressed,
such as preparation parameters, buffer layers, dopants, or
substitutions, etc. More importantly, much more attention
should be given to the design and construction of phase
boundaries as well as the relationships between strain and
electrical properties if subsequent breakthroughs are desired.
4.5.8. Poling Conditions. The optimized poling conditions
are a very important tool to improve the piezoelectric
properties of lead-based or lead-free ceramics,166,169,284,510−522
including poling temperatures, poling electric fields, dwell
times, etc. Recently, much attention has been given to the
effects of the poling conditions on the electrical properties of
lead-free ceramics, such as BaTiO3,45,512,513 Bi1/2Na1/2-
TiO3,513−519 and K1/2Na1/2NbO3.166,169,265,284,520−522 For
KNN ceramics, the poling conditions (especially poling
temperatures) become very important due to the intrinsic
characteristics of the O−T phase boundary with a
PPT.166,169,265,520−522 As far as KNN-based ceramics are
concerned, one usually chooses poling temperatures near its
phase transition temperature.169,265 For example, Du et al.169
and Wu et al.265 improved the d33 values of KNN-based
ceramics by optimizing the poling temperatures (Tp), that is,
the Tp is located at the phase transition temperatures.
According to such a regulation, the d33 value can be increased
greatly for KNN-based ceramics with O−T phase bounda-
ries.520 Morozov et al.521 also studied the influence of the
poling temperature on the piezoelectricity of Li-, Ta-, and Mn-
modified (K,Na)NbO3 ceramics with O−T phase boundaries,
showing that the low-signal dielectric and piezoelectric
properties in orthorhombic phase can be enhanced by poling
in tetragonal phase. Zhao et al.522 investigated the relationships
between 90° domain reorientations and poling fields of
(K,Na,Li)NbO3 ceramics by X-ray diffraction analysis, indicat-
ing that the 90° domain reorientation can be effected by
applying poling fields (5 kV/mm), finally leading to enhanced
piezoelectricity. Recently, Li and Wang et al.166 promoted the
enhanced piezoelectricity of KNN-based ceramics from 190 to
324 pC/N by the aging and repoling method and proposed that
both defect migration and rotation of spontaneous polarization
are responsible for such a phenomenon. Recently, we
investigated the effects of poling conditions on the piezo-
electricity of (1−x)(K 0 . 4 2 Na 0 . 5 8 )(Nb 0 . 9 6 Sb 0 . 0 4 )O 3 −
x(Bi0.5K0.5)0.90Zn0.10ZrO3 ceramics with R−T phase boundaries,
whereby a high d33 can be attained when Tp is located at its
TR−T. A very low poling electric field (>0.8 kV/mm) was
enough to warrant full polarization due to the involvement of
more polarization states.284 As a result, the optimization of
poling conditions becomes very important for further enhance-
ment of the piezoelectric activity of KNN-based ceramics and
should be given further attention.
4.5.9. Sintering Aids and Sintering Atmosphere.
Sintering aids can improve the electrical properties of KNN
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Table 21. Electrical Properties of KNN-Based Ceramics with Doping Oxides

material system density or relative density ε/εo d33 (pC/N) kp tan δ Qm ref
KNN−Bi2O3 99.3% 140 0.46 410 147
KNLN−CuO 4.33 g/cm3 1287 109 0.36 1023 530
KNN−CuO 98.9% 237 96 0.389 0.005 415 531
KNLNTS−Fe2O3 257 0.53 543
KNN−Fe2O3 97.5% 593 136 0.41 0.042 412 544
KNN−La2O3 93.3% 815 92 0.34 0.179 396 544
KNN−(La−Fe2O3) 96.7% 723 145 0.43 0.039 392 544
KNN−ZrO2 905 100 0.040 591
KNN−ZnO 97% 652 117 0.44 0.033 418 592
KNN−SnO2 98% 627 108 0.39 0.045 405 592
KNN−CdO 95.3% 493 107 0.42 0.040 406 592
KNN−CuNb2O6 4.47 g/cm3 92.5 0.40 1933 526
KNN−ZnO−SnO2 4.48 g/cm3 503 124 0.398 0.010 596
KNN−CuO−SnO2 97.8% 710 120 0.38 0.013 1040 597
KNNS−K4CuNb8O23−La2O3 4.376 g/cm3 160 0.38 283 593
KNN−MnO2−K5.4Cu1.3Ta10O29 4.65 g/cm3 300 90 0.40 0.003 1900 594
KNN−K5.4Cu1.3Ta10O29−CuO 97% 285 94 0.38 0.0018 3053 595

materials by the improvement in the densification and between the extrinsic factors and the piezoelectric properties of
microstructure.130,140,143,147,523−545 In recent decades, many KNN-based materials.
aids have been used to sinter KNN ceramics (refs 130, 140, 4.6.1. Density vs Electrical Properties. It is well known
143, 147, 523−546, 591, 601, and 602), including K4CuNb8O23 that densification of pure KNN ceramics is difficult due to their
(KCN), 130 K 5.4 CuTa 10 O 29 (KCT), 140,143,524 K 1.94 Zn 1.06 - poor sinterability and high volatility;3,121,127,137,249 thus, poor
Ta 5.19 O 15 (KZT), 525 CuNb 2 O 6 , 526 CuO, 145,527−531,602 d33 values are often observed by conventional solid-state
Mn3O4,532 MnO2,533,534 MoO3,535 ZnO,536−539 La2O3,540 methods.137,249 As a result, it is very important to understand
Bi2O3,147,541,542 Fe2O3,543,544 V2O5,545 and ZrO2.591 Sintering the relationships between density and piezoelectric activity of
aids have two main advantages for KNN materials: (i) KNN ceramics except for the phase boundaries,125 the
improving the density, such as KZT, KCN, etc.; and (ii) compositions,125 or other factors. Here we gave an example
enhancing electrical properties (e.g., d33, kp, Qm, etc.) due to and discussed the influence of the density on the d33 in a pure
their “softening” or “hardening” characteristics, such as CuO, KNN ceramic using different preparation methods, as shown in
KCN, KCT, etc. In addition, the electrical properties of KNN Table 22. It is clear that a pure KNN ceramic sintered in air has
materials could be improved by doping with two sintering
aids,593−597 such as K4CuNb8O23 and La2O3,593 MnO2 and Table 22. Relationship between Density and Piezoelectricity
K5.4Cu1.3Ta10O29,594 K5.4Cu1.3Ta10O29 and CuO,595 ZnO and of a Pure KNN Ceramic Obtained by Different Groups
SnO2,596 CuO and SnO2,597 etc. Table 21 shows the density relative d33
and electrical properties of KNN ceramics with doping preparation density (pC/
oxides.147,526,530,531,543,544,591−597 In particular, the ceramic material system method ρ (%) N) kp ref
matrixes used mainly involve a pure K0.5Na0.5NbO3 air sintered 4.30 95.3 110 0.39 121
KNN147,526,531,544,546,547,594−597 not those doped with other K0.5Na0.5NbO3 air sintered 4.26 94.4 80 137
components.530,543 As shown in Table 21, a higher d33 is K0.5Na0.5NbO3 air sintered 4.25 94.24 80 0.36 249
attained in the ceramics because of the improved density K0.5Na0.5NbO3 spark 4.47 >99.0 148 0.39 127
plasma
induced by the addition of oxides,147,530,542,591,593,596,597 and a sintering
higher Qm was also shown.147,526,531,542,543,546,547,593−597 In K0.5Na0.5NbO3 hot pressed 4.46 98.89 160 0.45 249
addition, the atmosphere during sintering is an important factor
to determine the electrical properties of KNN materials by
changing the microstructure (e.g., grain morphology598 and a lower density than one sintered by SPS or hot press
density599−601). Among sintering atmospheres, an oxygen methods;121,127,137,249 thus, higher d33 values are shown by SPS
atmosphere during sintering usually has a large effect on the or hot-pressed samples due to the improved density.127,249 In
electrical properties of KNN ceramics due to microstructure the past decade, some methods (e.g., sintering temper-
evolution.598−601 ature, 1 1 2 , 1 6 5 , 1 7 7 , 4 2 0 − 4 3 2 , 4 7 0 rapid sintering techni-
4.6. Extrinsic Factors que,127,447,450,451 the use of sintering aids (refs 130, 140, 143,
147, 523−545, and 602), and sintering atmosphere598−601)
In the last section, we illustrated the influences of intrinsic have been used to improve the density of KNN ceramics.
factors (i.e., crystalline structure, lattice parameters evolution, Among these methods, the main goal is to suppress the loss of
phase boundaries, etc.) and some special preparation alkali metals112,127,165,177,421−431,447,450,451,470 or the formation
techniques on the piezoelectric properties of KNN-based of liquid phases130,140,143,147,523−545 during the sintering
materials. In addition, extrinsic factors (i.e., density, micro- process. The piezoelectric activity of KNN materials can
structure evolution, domain structure, etc.) also play a crucial often be enhanced by increasing their den-
role in the development of technological applications. As a sity.127,147,249,530,542,591 However, it was also found that the
result, we briefly provide an overview of the relationships piezoelectric activity of KNN-based materials was not only
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Figure 21. SEM images of KNN-based ceramics with R−T phase boundaries reported by us.110,112,115,114,117,285
dependent on the density but also very sensitive to fluctuations
of composition (e.g., the degree of volatilization) when the
compositions are situated at the phase boundary regions.125 As
a result, other factors should be also considered except for the
density.
4.6.2. Grain Morphology vs Electrical Properties. It is
usually accepted that the microstructure (e.g., grain morphol-
ogy) of KNN-based materials can be modulated by a sintering
aid,130,140,143,147,523−545 the use of new preparation techni-
ques,127,249,447,450,451 various sintering atmospheres,598 and
others. Many researchers have improved the sinterability of
KNN-based materials using different sintering
aids145,413,528,533,534,537,539,604 (e.g., CuO,145,413,528 NiO,603
ZnO,537,539 MnO,604 and MnO2533), and the existence of A-
site vacancies can offset the formation of the hygroscopic
secondary phases because these chemical elements substitute
the B site in ABO3.124 In addition, sintering aids are often used
to densify KNN ceramics by introducing a liquid
phase 130,140,145,143,147,523−545 or a “transient” liquid
phase,124,132,537 and the grain morphologies can be also
controlled by changing the concentration of sintering
aids.124,132,537 In particular, bimodal grain size distributions
were often observed in KNN-based ceramics doped by
oxides.132,539 It was proposed that the general grain growths
observed in oxide-doped samples should be attributed to
enhanced atomic mobility,132,539 dramatic grain growth can be
induced by the difference in surface free energies between large
grains and small grains,3 and then bimodal grain sizes can be
facilitated and accelerated due to the presence of a liquid phase.
However, piezoelectric activity will usually be degraded by the
addition of sintering aids because a material’s phase transition
temperature deviates to room temperature.145,537,413,603,604 In
addition, the piezoelectric activity of KNN-based ceramics is
closely related to their average grain sizes.132,605 Also, the grain
growth behavior of a pure KNN ceramic can be controlled by
different sintering atmospheres because of the critical driving
force for 2D nucleation-controlled grain growth caused by their
different edge free energies.598 As a result, the grain
morphologies of KNN-based ceramics can be modified by
different methods.
2582
Review
It was previously reported that abnormal grain growth
(AGG) was usually present in KNN-based ceramics, leading to
degradation of their piezoelectric proper-
ties.105,114,173,269,284,285,606 Recently, bimodal grain size distri-
bution has also been observed in KNN-based ceramics with R−
T phase coexistence108−118,285 (see Figure 21). However, a
large d33 of >400 pC/N can be attained, which seems to be at
odds with the reported results.105,173 For KNN-based ceramics
with R−T phase boundaries, the phase boundary should play a
critical role in the piezoelectric properties of KNN-based
ceramics; thus, the negative effect of AGG can be almost
neglected or decreased. As a result, the piezoelectric activity of
KNN-based materials was more sensitive to the phase boundary
with respect to the negative effect of AGG when the
compositions were situated at the R−T phase boundary
regions.108−118,285 Preparation of R−T KNN-based ceramics
with a unimodal grain size distribution is necessary in order to
further promote their piezoelectric activity. Some methods may
decrease the extent of AGG in KNN materials, such as the
particle size (nanopowder) of calcined powders, milling
strategies, etc.607
Recently, it was shown that grain morphologies can be
controlled by developing KNN-based low-dimensional materi-
als using different preparation techniques,271,608−613 strongly
affecting their electrical properties.271,610−613 For example, Li et
al. reported that one-dimensional KNN nanorods fabricated by
a molten-salt method possess a high piezoelectric constant
(d33* ≈ 230 pm/V),612 the K/Na ratios of one-dimensional
KNN nanorods seriously affect their piezoelectricity, and
moreover the phase boundary is also obviously different from
that of KNN bulk.271 In addition, higher d33* values of 180 pm/
V were also shown in vertically aligned lead-free (K0.6Na0.4)-
NbO3 nanorod arrays via the facile hydrothermal method.613
Thus, control of morphology is an efficient way to promote the
piezoelectric properties of KNN-based materials.271,610−613
4.6.3. Domain Structure vs Electrical Properties.
Domain structure can determine the piezoelectric properties
of a ferroelectric material,446,268,269,406,614−622 that is, the
electrical properties of a ferroelectric material can be modulated
by changing the domain structure as well as domain−wall
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Figure 22. (a) Relationship between phase boundary type, piezoelectric constant, and Curie temperature,12,90−201 and (b) comparison of the
piezoelectric properties of PZT and KNN.
rotations. As a result, it is necessary to clarify the ferroelectric
domain structure of KNN-based materials with the phase
boundary compositions in order to further understand its
nanoscale properties and improve its piezoelectricity.
The domain structure of KNN-based materials can be well
identified by a number of measurement techniques (see section
3). For example, the domain patterns concerning 60° and 90°
domain walls were observed in pure or Mn-doped KNN single
crystals by polarizing optical microscopy, and the domain width
was found to be a few tens of micrometers.614 The unpoled
KNN ceramics possess only 90° and 180° domain walls,269
while the domain structure changes when Li is doped to KNN,
that is, the domains (e.g., 60°, 90°, and 180°) and S-type
domain walls were simultaneously observed in a grain.615 In
addition, some researchers have investigated the domain
structure of KNN-based materials with the phase boundary
compositions.406,616 For example, the phase transition temper-
atures (e.g., TR−O, TO−T, and TC) of KNN single crystals were
graphically confirmed by the changes of the domain structures
under different temperatures.406 The coexisting tetragonal and
orthorhombic domains were vividly observed in one grain of
K0.44Na0.52Li0.04Nb0.86Ta0.1Sb0.04O3 by piezoresponse force
microscopy, providing a basis for the understanding of the
PPT of KNN-based materials.616 As a result, the domain
structure can allow the characterization of the phase structure
of KNN-based materials.
There is a close relationship between domain structure and
phase structure of KNN-based materials, and the phase
structure can determine its piezoelectric activity.268,617−622 As
a result, the piezoelectric properties of KNN-based materials
can be tailored by varying their domain structure. Recently, the
relationships between domain structure and piezoelectricity of
KNN-based materials have been studied by considering the
changes in domain structure. Zhang et al.617 investigated the
evolution of domain structure in hot-pressed KNN ceramics
before and after poling, and the irreversible domain wall
motions were found to strongly contribute to the piezoelectric
coefficient of the hot-pressed KNN ceramics. Transmission
electron microscopy was used to in situ identify the evolutions
of the domain morphologies and phase structures under driving
electric fields (E) of 0.948(K0.5Na0.5)NbO3−0.052LiSbO3, and
it was found that the enhanced piezoelectric properties result
from a tilted monoclinic phase from O−T for E > 14 kV/cm.618
For O−T (Na,K,Li)(Nb,Ta,Sb)O3 ceramics, the nanodomains
(e.g., 20−50 nm width) generated enhanced piezoelectric
properties due to the reduced domain wall energy induced by
2583
Review
the disappearance of the polar anisotropy by means of
transmission electron microscopy, which also confirms the
different domain structure between PPT and MPB,268 and the
R−T phase boundary is also confirmed by the tweed-like
domain morphology.619 In addition, the relationships between
domain patterns and time-aging stability of d33 were illuminated
in (K0.5Na0.5)1−xLixNbO3 ceramics, and the involved 180°
domains cause the degradation and time-aging instability of
piezoelectric properties.620 It was also found that domain size
seriously affects the electrical properties of KNN-based
materials. For example, the decreased domain sizes can reduce
the coercive field of Li0.02(K0.45Na0.55)0.98NbO3 ceramics,621 and
both curved domain stripes and larger average domain width
were found to improve the piezoelectric properties of
(K0.5Na0.5)0.965Li0.035(Nb0.8Ta0.2)O3 ceramics with O−T phase
coexistence.622 As a result, the evolutions of the piezoelectric
properties can be described and explained by characterizing
their domain structure, and correspondingly the piezoelectricity
can be promoted by varying the domain types and sizes.
In this section, the electrical properties of KNN-based
materials could be further improved by microstructure variation
using tools besides the phase boundary. Among those tools,
their electrical properties can best be improved by controlling
the microstructure evolution (e.g., density, grain size and
morphology, domain structure, etc.). In addition, multiple tools
are always used together to modify the KNN-based materials.
As a result, more consideration should be given to these
supplementary tools for preparing KNN materials.
5. RELATIONSHIP BETWEEN PHASE BOUNDARIES
AND PIEZOELECTRICITY
Generally speaking, the piezoelectric activity of KNN-based
ceramics can be enhanced in different degrees by constructing
phase boundaries and modifying the microstructure of a
material, while its piezoelectric activity is strongly sensitive to
the phase boundary types. In this section, we further clarify the
relationships between phase boundary and piezoelectric activity
of KNN-based materials, addressing the weakness and the
corresponding solution methods. Tables 1−12 display the
influences of the phase boundary types on the piezoelectric
activity of KNN-based materials. There is a progressive
development from O−T, to R−O, to R−T in chronological
order, and the trend of d33 is R−O < O−T ≤ R−T according to
the piezoelectric activity, as shown in Tables 1−12. At the same
time, it is much more difficult and complicated to construct R−
T phase boundaries with respect to R−O and O−T, as the R−
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Figure 23. (a) Articles concerned with lead-free piezoelectric materials in refereed journals published between 2010 and 2014 obtained from ISI Web
of Science using the keywords “lead-free piezoelectric” and “strain”. (b) Relative amounts of several kinds of lead-free piezoelectric materials in strain
investigations.
T phase boundary can be only formed by adding two or more
additives.106−113,256,277,284,285 In addition, the interrelationships
among different phase boundary types were also established,
and the methods to construct the R−O and O−T phase
boundaries provide a solid practical and theoretical basis for
designing the corresponding R−T, that is, the R−T phase
boundary can be induced by combining two kinds of
boundaries (R−O and O−T) using the optimum additives.
Figure 22a shows the piezoelectric constant, phase boundary
types, and Curie temperature of KNN-based ceramics, as
collected from a number of studies (refs 12, 17, 97, 101, 102,
104, 106−118, 166, 201, and 266−285). The types of phase
boundaries strongly affect the d33 value of KNN materials: R−
O ceramics possess a poorer d33 with respect to those with R−
T and O−T, the O−T ceramics have a wide d33 distribution
from 200 to 350 pC/N, and a large d33 of >330 pC/N is usually
induced in R−T ceramics. In addition, it was also found that
the piezoelectric activity of R−T KNN-based ceramics can be
comparable to part-PZT ceramics. However, during the
development of KNN-based materials a general trend has
emerged whereby the d33 value is enhanced by sacrificing a
material’s TC, and the ceramics with a large d33 (>330 pC/N)
always have a low TC (<300 °C). As a result, the application
temperature range of KNN-based ceramics should be
considered when the phase boundaries are constructed, and it
is necessary to choose additives that increaseor at least do
not significantly reduceTC.108,109 We also compared KNN
with PZT in terms of their d33 and TC, as shown in Figure 22b.
For TC > 200 °C, the d33 of KNN-based ceramics has been
comparable or even superior to PZT-based ceramics. As a
result, we believe that KNN-based lead-free piezoceramics can
replace PZT in some applications.
6. APPLICATIONS OF KNN-BASED MATERIALS
The excellent piezoelectric properties of KNN-based materials
result in some practical applications (e.g., piezoelectric energy
harvesting, piezoelectric actuators, etc.), similar to PZT
ceramics. In this section, we pay special attention to their
applications in the field of piezoelectric energy harvesting and
piezoelectric actuators because this review mainly concerns the
relationships between phase boundary types and piezo-
electricity. In addition, other practical applications are also
briefly mentioned.17,120
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Review
6.1. Piezoelectric Energy Harvesting
So-called “energy harvesting” devices have attracted much
attention because energy can be generated from renewable
sources (e.g. temperature, vibration, air flow, etc.), with the
hope of solving the energy crisis if these devices can be
developed and made practical.623,624 Among these energy
harvesting devices, piezoelectric energy harvesting devices can
convert mechanical energy into electrical energy; moreover,
their energy density is usually superior to other energy
devices.625−628 Since piezoelectric nanogenerators fabricated
by piezoelectric zinc oxide nanowire arrays were first reported
for the direct energy conversion from mechanical motion to
electrical power,624 much attention has been focused on
investigations into piezoelectric energy harvesting devices. In
the past, most piezoelectric energy harvesting devices were
fabricated using PZT-based materials due to their promising
electrical properties.625,626,628,629 Recently, energy harvesting
devices have been fabricated using KNN-based materials,630−632
motivated by environmental concerns over lead-containing
PZT-based materials.625,626,628,629 For example, energy harvest-
ing devices based on (K0.5Na0.5)0.97(Nb0.96Sb0.04)O3 ceramics
doped with 0.2 wt % CeO2 were fabricated, possessing
optimum output voltage (24.6 mVrms) and power (0.839
μW) under an external vibration acceleration of 0.7 g.630 More
recently, a large-area nanocomposite generator device was
fabricated using alkaline niobate-based particles and copper
nanorod fillers, providing a maximum output of up to 140 V
and 8 μA (∼0.5 mW).632
6.2. Piezoelectric Actuator
It is well known that actuator applications require electro-
mechanical coupling providing high strain with high force, and
this requirement can be realized by piezoelectric materials that
allow direct conversion between electrical and mechanical
energy.17,120 Currently, the piezoactuator markets were
dominated by PZT materials in the form of the ceramics or
thin films,633 and lead-free piezoelectric materials concerning
strain are also experiencing gradual growth due to environ-
mental regulations,12,66−68,93,162,178,634 as shown in Figure 23a.
Recently, strain investigations have triggered strong interest in
the field of lead-free piezoelectrics,12,66−68,93,162,178,634 since a
high unipolar strain value of ∼0.45% was first reported in BNT-
based ceramics under a high driving electric field of ∼8 kV/
mm.68,634 It is thought that, for the first time, the electrical
properties (strain) of lead-free piezoelectrics have become
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Chemical Reviews
Figure 24. Unipolar strain in 0.965K0.45Na0.55Nb0.98Sb0.02O3−0.035Bi0.5Na0.5Zr0.85Hf0.15O3 ceramics, measured at 10 Hz and room temperature.
superior or comparable to those of lead-based examples.68,634
We can see from Figure 23b that most research has focused on
strain investigations with BNT-based materials because of its
high strain values. However, issues related to their transfer into
practical applications need to be resolved despite a high strain
in the mentioned ceramics,635 that is, a high driving electric
field is often required to warrant a large strain,68,634 and the
strain hysteresis exhibits a strong nonlinearity.68,634
Recent research results show that KNN-based ceramics can
effectively address two of these issues,93,162,178,265,270,278,285,636
where a slimmer strain hysteresis and a relatively high unipolar
strain value under a low driving electric field can be
attained.93,162,178,265,270,278,285,636 In addition, a high unipolar
strain was also observed in KNN-based materials.93,178,270,278 In
our group, 0.965K0.45Na0.55Nb0.98Sb0.02O3−
0.035Bi0.5Na0.5Zr0.85Hf0.15O3 ceramic systems have been
recently developed (see Figure 24), and a high unipolar strain
and a slimmer strain hysteresis compared with the BNT-based
materials68,634,635 can be simultaneously observed, due to the
involvement of phase boundaries, as shown in Figure 24. There
are few reports of such a high unipolar strain value in KNN-
based ceramics, which is two times as high as those reported for
(Li, Ta, Sb)-doped KNN textured ceramics.12 Recently, Li et
al.636 reported that the unipolar strain of CaZrO3 and MnO2
comodified (K,Na,Li)(Nb,Ta)O3 ceramics shows fatigue-free
(only small degradation within 3%) during 107 cycles under a
field amplitude of 2 kV/mm, which results from the “softening”
effect. Rubio-Marcos et al.93 developed a high strain value with
Smax as high as 0.17% at 3 kV mm−1 in the (K0.44Na0.52Li0.04)
(Nb0.86Ta0.10Sb0.04)O3 microfiber ceramics. These results
indicate that KNN-based materials are the most promising
candidates in the field of lead-free piezoelectric actua-
tors.265,270,278,285,636
In the past, transducers,148,637,638 buzzers,159,639 surface
acoustic wave filters,640 and other devices have been developed
using KNN-based materials. In addition, the performance of
some devices is comparable to those fabricated by PZT-based
materials. For a detailed introduction of applications, the reader
is referred to recent works reported by Rödel and Jo.17,120
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Review
7. OUTLOOK AND FUTURE WORK
We systematically reviewed the construction of phase
boundaries as well as the related physical mechanisms in
KNN-based materials by comprehensively analyzing the recent
advances in the field as well as the achieved results. Although
the piezoelectric activity of KNN-based materials can be
promoted by constructing different phase boundaries as well as
other supplementary tools, some issues still need to be
addressed before large-scale application can be realized.
According to our review of the recent advances in KNN-
based materials, a number of recurring problems haunt
researchers in the field, e.g., how to design new phase
boundaries, identify the phase compositions, investigate the
interrelationships between different phase boundary types,
phase compositions, and piezoelectric properties, etc. In order
to clearly solve these issues, future work will most likely focus
on the following challenges.
7.1. Designing New Phase Boundaries
Although the R−T phase boundary of KNN-based materials
can more significantly improve the piezoelectric activity with
respect to other phase boundary types, its piezoelectric activity
continues to catch up to those of PZT ceramics in terms of
meeting the requirements of different applications. As a result,
it is necessary to further increase the piezoelectric activity of
such materials by developing new phase boundaries similar to
those of PZT.
7.2. Analyzing Phase Compositions
Phase composition identification is critical to establishing the
relationships between phase boundaries and piezoelectric
properties, providing us with a guide to refining the phase
boundaries and further promoting a material’s piezoelectricity.
In addition, the relationships between domains and phase
boundaries should be established; then the piezoelectric activity
can be modified by varying the domain structure.
7.3. Physical Origin of High Piezoelectricity
It is very important to understand the physical origin of high
piezoelectricity in order to investigate the relationships between
the phase boundaries, phase compositions, and piezoelectric
properties of KNN materials. The different phase boundaries
can be constructed by doping additives, then the phase
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Chemical Reviews Review

compositions concerning phase boundaries can be optimized Jiagang Wu received his B.S. degree from Sichuan University in 2003
by refining the types and concentration of the additives, and and Ph.D. degree from Sichuan University in 2008 and worked as a
finally the piezoelectric activity can be enhanced by modifying Singapore Millennium Postdoctoral Fellow (SMF-PDF) at the
the phase compositions. National University of Singapore from 2008 to 2010 (2 years). He
7.4. Intrinsic Characteristics of Phase Boundaries has been an Associate Professor at the Department of Materials
Science, Sichuan University, since 2011. His main research interest is
The intrinsic differences between different phase boundary
composition design and property modification of ferroelectric/
types (e.g., O−T, R−O, R−T, etc.) and the intrinsic
piezoelectric/multiferroic materials.
characteristics of MPB and PPT were studied by investigating
the temperature-dependent domain structure.
7.5. Investigating the Stability of Piezoelectricity
The greatest challenge for KNN-based materials is how to
improve the stability of piezoelectricity. In the past, there was
conflict between piezoelectricity and its stability, that is, if a
large d33 induced by PPT phase boundaries shows strong
temperature dependence. As a result, phase boundaries with
MPB characteristics may be an effective way to solve this issue.
It is still an open question as to whether KNN-based materials
possess phase boundaries with MPB characteristics.
7.6. Other Issues
Potassium−sodium niobate lead-free piezoceramics will be a
promising lead-free materials for actuator applications. It was
wondered whether a large strain can be induced by phase Dingquan Xiao received his B.S. degree from Sichuan University in
transitions. As a result, it may be very interesting to investigate 1968 and M.S. degree from Sichuan University in 1980, studied at the
the relationships between phase transitions and strains of Queen Mary University of London from 1980 to 1982, and worked a
potassium−sodium niobate materials. senior visiting scholar at the University of Pennsylvania in 1990 and
the University of Houston in 1998. He has worked at Sichuan
8. CONCLUSIONS University since 1983. Currently, he is a Professor in the College of
High-performance lead-free piezoceramics have become an Materials Science and Engineering of Sichuan University. His main
international research frontier in the fields of high technology research interests include ferroelectric/piezoelectric ceramics, dielec-
and new materials. In this review, we systematically reviewed tric materials, ferroelectric thin films, ecomaterials, and electrochemical
the developments of phase boundaries as well as the techniques. He is a member of the Chinese Materials Research Society
piezoelectric properties of KNN-based materials, and some and the Chinese Physics Society.
suggestions for the future development of KNN materials were
also addressed. In the past decade, piezoelectric properties have
been greatly increased by constructing phase boundaries, and
piezoelectricity comparable to those of PZT-based materials has
been achieved. As a result, we believe that KNN-based lead-free
ceramics will gain wide practical application in the near future.

AUTHOR INFORMATION
Corresponding Author
*E-mail:wujiagang0208@163.com and msewujg@scu.edu.cn.
Notes
The authors declare no competing financial interest.
Biographies
Jianguo Zhu received his M.S. degree from Sichuan University in 1987
and Ph.D. degree in materials science from Sichuan University in 1998.
He has worked at Sichuan University since 1987. Currently, he is
Professor and Dean of the College of Materials Science and
Engineering of Sichuan University. His research activities are
ferroelectric/piezoelectric ceramics, dielectric materials, and ferro-
electric thin films. He is a member of the Chinese Materials Research
Society and the Sichuan Silicate Society.

ACKNOWLEDGMENTS
We gratefully acknowledge the support of the National Science
Foundation of China (NSFC Nos. 51102173, 51272164,
51332003, and 51472169), the Fundamental Research Funds
for the Central Universities (2012SCU04A01), introduction of
2586 DOI: 10.1021/cr5006809
Chem. Rev. 2015, 115, 2559−2595
Chemical Reviews
talent starting funds of Sichuan University (2082204144033),
and the College of Materials Science and Engineering of
Sichuan University. We are also thankful to a number of
researchers who provided help during our research: Xiaojie Lou
and Xiangjian Wang (Xi’an Jiaotong University), Hui Wang
(Sichuan University), Ruishi Xie (Southwest University of
Science and Technology) and Hao Tian (Harbin Institute of
Technology). Finally, we would like to sincerely thank the
reviewers for valuable suggestions.
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DOI: 10.1021/cr5006809
Chem. Rev. 2015, 115, 2559−2595